CA1292662C - Process for forming deposited film - Google Patents
Process for forming deposited filmInfo
- Publication number
- CA1292662C CA1292662C CA000534808A CA534808A CA1292662C CA 1292662 C CA1292662 C CA 1292662C CA 000534808 A CA000534808 A CA 000534808A CA 534808 A CA534808 A CA 534808A CA 1292662 C CA1292662 C CA 1292662C
- Authority
- CA
- Canada
- Prior art keywords
- forming
- deposited film
- film
- substrate
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/24—Deposition of silicon only
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0227—Pretreatment of the material to be coated by cleaning or etching
- C23C16/0236—Pretreatment of the material to be coated by cleaning or etching by etching with a reactive gas
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/448—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
- C23C16/452—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials by activating reactive gas streams before their introduction into the reaction chamber, e.g. by ionisation or addition of reactive species
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02367—Substrates
- H01L21/0237—Materials
- H01L21/02422—Non-crystalline insulating materials, e.g. glass, polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02367—Substrates
- H01L21/02428—Structure
- H01L21/0243—Surface structure
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02524—Group 14 semiconducting materials
- H01L21/02532—Silicon, silicon germanium, germanium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/0257—Doping during depositing
- H01L21/02573—Conductivity type
- H01L21/02576—N-type
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/0257—Doping during depositing
- H01L21/02573—Conductivity type
- H01L21/02579—P-type
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02612—Formation types
- H01L21/02617—Deposition types
- H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S117/00—Single-crystal, oriented-crystal, and epitaxy growth processes; non-coating apparatus therefor
- Y10S117/903—Dendrite or web or cage technique
- Y10S117/904—Laser beam
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S117/00—Single-crystal, oriented-crystal, and epitaxy growth processes; non-coating apparatus therefor
- Y10S117/905—Electron beam
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S438/00—Semiconductor device manufacturing: process
- Y10S438/913—Diverse treatments performed in unitary chamber
Abstract
ABSTRACT OF THE DISCLOSURE
A process for forming a deposited film comprises the steps of:
(a) preparing a substrate for deposited film formation by selectively irradiating the surface of a base member with an energy beam of an electromagnetic wave or electron beam through atmosphere of a reactive gas or a gas having etching action to provide regions where crystal nuclei are selectively formed scatteringly on the surface;
(b) forming a deposited film on said substrate by introducing an activated species (A) formed by decomposition of a compound (SX) containing silicon and a halogen and an activated species (B) formed from a chemical substance (B) for film formation which is chemically mutually reactive with said activated species (A) separately from each other into a film forming space in which said substrate is previously arranged to effect chemical reaction therebetween; and (c) introducing into said film forming space during the film forming step (b) a gaseous substance (E) having etching action on the deposited film to be formed or a gaseous substance (E2) capable of forming the gaseous substance (E) and exposing the deposited film growth surface to the gaseous substance (E) to apply etching action on the deposited film growth surface, thereby effecting preferentially crystal growth in a specific face direction.
A process for forming a deposited film comprises the steps of:
(a) preparing a substrate for deposited film formation by selectively irradiating the surface of a base member with an energy beam of an electromagnetic wave or electron beam through atmosphere of a reactive gas or a gas having etching action to provide regions where crystal nuclei are selectively formed scatteringly on the surface;
(b) forming a deposited film on said substrate by introducing an activated species (A) formed by decomposition of a compound (SX) containing silicon and a halogen and an activated species (B) formed from a chemical substance (B) for film formation which is chemically mutually reactive with said activated species (A) separately from each other into a film forming space in which said substrate is previously arranged to effect chemical reaction therebetween; and (c) introducing into said film forming space during the film forming step (b) a gaseous substance (E) having etching action on the deposited film to be formed or a gaseous substance (E2) capable of forming the gaseous substance (E) and exposing the deposited film growth surface to the gaseous substance (E) to apply etching action on the deposited film growth surface, thereby effecting preferentially crystal growth in a specific face direction.
Description
izgZ6~j2 Process for Forming Deposited Film BACKGOUND OF THE INVENTION
Field of the Invention This invention relates to a process suitable for forming a functional deposited film containing silicon, particularly a polycrystalline silicon deposited film for use in semiconductor devices, photosensitive device, line sensors for image input, image pick-up devices, etc.
Related Background Art Heretofore, a process for forming a polycrystalline or monocrystalline semiconductor layer composed of coarse grains by exposing a polycrystalline or amorphous semiconductor layer on an insulating substrate to an energy beam has been proposed as prior art. For example, a polycrystalline or monocrystalline silicon layer composed of coarse grains can be formed by coating a silicon substrate with an insulating film of SiO2 or SiN, depositing a polycrystalline layer thereon by CVD in reduced pressure or normal pressure or by plasma CVD, and subjecting the polycrystalline layer to annealing by irradiation of a continuous laser beam or electron beam. However, it is difficult to control crystal grain size, crystal grain size distribution, crystal lZ926~j2 1 grain site, etc. of polycrystalline silicon or crystal face orientation according to the piror art process.
Therefore, in semiconductor devices where semiconductor elements are formed on a semiconductor substrate 5 as described above, fluctuation and reliability in their characteristics have been thus problems.
According to another prior art process, a polycrystalline layer composed of coarse grains or a monocrystalline layer is formed by forming regular grooves tgratings) on an insulating film surface, depositing a polycrystalline or amorphous silicon layer thereon, and annealing the layer (graphoepitaxial process).
However, this process has a poor reproducibility and the crystal face orientation cannot be completely controlled. Thus, a novel process for, depositing a film free from these problems has been desired.
SUMMARY OF THE INVENTION
The primary object of the present invention is to provide a novel process for forming a polycrystalline silicon deposited film free from the problems of the prior art processes as described above and not based on the conventional process.
Another object of the present invention is to solve the said problems and provide a process for forming a deposited film by which a polycrystalline film of good quality and uniform crystal face iZ9Z6~Z
I orientation can be obtained.
Still another object of the present invention is to provide a process for forming a polycrystalline deposited film, which comprises selectively irradiating a substrate with an energy beam obtained by previously conversing energy such as an electromagnetic wave such as light, microwave, etc., and an electron beam etc.
to limit the sites of crystal nucleation on the substrate, and effecting film formation while controlling crystal grain size of polycrystal.
Yet another object of the present invention is to provide a process for forming a polycrystalline deposited film which is suitable for enlargement of the area of the film and can easily accomplish improvement of productivity and bulk production of the film, while attempting to improve the characteristics of the film formed, the film forming speed and reproducibility and also to uniformize film quality.
According to the present invention, there is provided a process for forming a deposited film comprising the steps of:
(a) preparing a substrate for deposited film formation by selectively irradiating the surface of a base member with an energy beam of an electro-magnetic wave or electron beam through atmosphereof a reactive gas or a gas having etching action to provide regions where crystal nuclei are selectively 12~Z6~2 I formed scatteringly on the surface;
(b) forming a deposited film on said substrate by introducing an activated species (A) formed by decomposition of a compound (SX) containing silicon and 5 a halogen and an activated species (B) formed from a chemical substance (B) for film formation which is chemically mutually reactive with said activated species (A) separately from each other into a film forming space in which said substrate is previously arranged to effect chemical reaction therebetween; and (c) introducing into said film forming space during the film forming step (b) a gaseous substance (E) having etching action on the deposited film to be formed or a gaseous substance (E2) capable of forming the gaseous substance (E) and exposing the deposited film growth surface to the gaseous substance (E) to apply etching action on the deposited film growth surface, thereby effecting preferentially crystal growth in a specific face direction.
~RIEF DESCRIPTION OF THE DRAWINGS
Figs. 1 and 2 are each schematic views illustrating the main part of a deposited film forming device for embodying the process of the present invention.
129Z66;~
I Figs. 3, 4 and 6 are each schematic views illustrating the substrate for deposited film formation used in Examples.
Fig. 5 is a schematic illustration of the main part of the electron beam irradiating device which is a substrate preparing device used in Example.
DESCRIPTION OF THE PREFERRED EMBODIMENT
At first, a procedure for selectively providing crystal nucleation regions (nucleation surface) on a substrate beforehand will be described below, and then a procedure capable of controlling the crystal face direction (orientation) and polycrystal grain size using the substrate will be described.
Crystal nucleation regions can be selectively formed on a substrate, for example, i) by locally and spotwise irradiating the substrate with an energy beam of a convergent electromagnetic wave such as light, microwave, etc. or an electron beam, thereby locally forming a deposited film on the substrate, or ii) by locally etching the substrate, thereby making the substrate surface irregular, or iii) by locally and spotwise irradiating the substrate with an energy beam, thereby crystallizing parts of the substrate surface or iv) effecting isomerization treatment of the substrate surface, thereby changing the adsorption characteristics or chemical activity of the substrate 12~Z66Z
I surface; that is, providing locally a surface-energetic or physical localization on the substrate. Specifically, as the above process (i), there is mentioned, for example, a process comprising irradiating a substrate 5 locally and spotwise through reactive gases with an energy beam obtained by converging an electromagnetic wave such as light, microwave, etc. or an electron beam to locally deposit a deposit film onto the substrate.
As the above process (ii), there is mentioned, for example, a process in which the substrate surface is locally made irregular by using a reactive etching gas in place of reactive gases, or a process in which a positive type resist is applied to the substrate and the substrate is exposed locally to an energy beam to make the substrate surface irregular. As the above processes (iii) and (iv), there is mentioned, for example, a process in which an amorphous thin film is deposited on a substrate by a known method, for example, by RF glow discharge, vacuum vapor deposition, sputtering or light CVD
beforehand, and then the substrate is exposed locally to an energy beam to effect crystallization or isomerization, or a process in which a thin film of an organic compound is deposited on a substrate by interfacial adsorption such as by monomolecular layer build-up (LB method), gaseous phase adsorption, liquid phase adsorption, etc. or by electrolytic polymerization, vapor deposition or sputtering, and then the substrate ~2~2t;t`2 1 is exposed locally to the energy beam to effect isomerization or crystallization. Or a substrate of polymeric material is exposed locally to an energy beam to effect isomerization to form nucleation regions.
Next, process for forming a film while controll-ing thP orientation, grain size and grain size distribution of the crystal by using a substrate having crystal nucleation regions provided selectively thereon according to the above processes will be described below.
In the present invention, as a first step, a substrate having a nucleation surface provided , _ /
/
lZ9Z6~Z
I selectively on the surface thereof is previously arranged in a film forming space for formation of a deposited film [Step (a)).
Next, an activated species (A) formed by decomposition of a compound (SX) containing silicon and a halogen and an activated species (B) formed from a chemical substance (B) for film formation which is chemically mutually reactive with the activated species (A) are introduced separately from each other into the film forming space to effect chemical reaction therebetween, thereby forming a deposited film on the substrate [Film forming Step (b)).
During the film forming step (b), a gaseous substance (E) having etching action on the deposited film to be formed or a gaseous substance (E2) capable of forming the gaseous substance (E) are introduced into the film forming space and the deposited film growth surface is exposed to the gaseous substance (E) to apply etching action on the deposited film growth surface, thereby effecting preferentially crystal growth in a specific face direction ~Step (c)~.
As described above, by providing the above steps (a)- (c) film formation can be effected while 25 desirably controlling the orientation, crystal grain size and grain size distribution and exhibiting the 129Z6~2 I technical advantage as described below.
The technical advantage accomplished according to the process of the present invention is that the deposited film formed in the copresence of an active 5 species (A) formed by decomposition of a compound containing silicon and halogen and another species (B) formed from a chemical substance for forming a film in a film-forming space in place of generating a plasma is insusceptible to adverse effects of the plasma.
Another advantage of the present invention is that a stable CVD process can be provided since the atmosphere temperature of the film forming space and the substrate temperature can be desirably controlled.
Still another advantage of the present process is accomplished by use of an active species previously activated in a different activation space from the film-forming space. That is the film-forming speed can be made drastically higher and the substrate temperature for forming a deposit film can be made much lower than the conventional CVD process while film characteristic of good quality can be obtained. Furthermore, there can be mentioned the advantage that a crystalline film can be formed having a specific crystal face orientation, that is, a film of good quality with a specific orientation of high degree and uniform grain size by the I etching effect of the gaseous material (E) having etching action.
The compound (SX) containing silicon and halogen to be introduced into the activation space (A) in the present invention, includes for example, linear or cyclic silane compounds, part or whole of whose hydrogen atoms are substituted with halogen atoms, are used. Specifically, linear silicon halides represented by SiuY2u+2, where u is an integer of 1 or more, Y is at least one element selected from F, Cl, Br and I, cyclic silicon halides represented by SivY2v, where v is an integer of 3 or more and Y has the same meaning as defined above, and linear or cyclic compounds represented by SiUHxYy, where u and Y have the same meaning as defined above and x + y = 2u or 2u + 2. More specifically, gaseous or reading gasifying compounds such as SiF4, (SiF2)5, 2 6 2)4' Si2F6, Si3F8, SiHF3, SiH2F SiCl (SiC12)5, SiBr4, (SiBr2)5, Si2C16, Si2Br6, SiHC13, 20 SiH3Cl, SiH2C12, SiHBr3, SiHC13, Si2C13F3, etc. can be enumerated.
In order to form an active species (A), silicon simple substance and other silicon compounds, hydrogen, halogen compounds (for example, F2 gas, C12 gas, gasified Br2,I2, etc.), etc. can be used together, if necessary, in addition to the compound containing silicon and halogen (SX).
6~;2 I In the present invention, the active species (A) is formed in the activation space (A) by an activation energy such as an elec~ric energy, for example, microwave, RF, low frequency wave, DC, etc., a thermal energy such as heater heating, infrared heating, etc., a photo energy, etc. in view of various given conditions and apparatuses.
As the chemical substance for forming a film to form the active species ( B ) in the activation space 10 (B) hydrogen gas and/or a halogen compound (for example, F2 gas, C12 gas, gasified Br2,I2, etc.) can be advantageously used. In addition to the chemical substance for forming a film, an inert gas such as helium, argon, neon, etc. can be used. When a plurality of these chemical substances for forming a film are used, they can be introduced in a gaseous state into the activation space (B) after mixing them in advance, or these chemical substances for forming a film can be separately introduced into the activation space 20 (B) from their independent supply sources, or introduced into the respective, independent activation spaces to make individual activations.
In the present invention, a mixing ratio of the active species (A) to the active species (B) to 25 be introduced into the film forming space is determined, as desired, in view of the film-forming conditions, lZgZ662 I kinds o the active species, etc., and is preferably 10:1 to 1:10 (introducing flow rate ratio), more preferably 8:2 to 4:6.
-20~
lZ926~:Z
1 Also, the deposited film formed according to the present inven~ion can be doped with the so-called impurity element used in the field of semiconductor during or after film formation. As the impurity element to be used, there may be employed, as p-type impurity, an element belonging to the group IIIA of the periodic table such as B, Al, Ga, In, Tl, etc. and, as n-type purity, an element belonging to the group VA of the periodic table such as P, As, Sb, Bi, etc. as suitable ones. Particularly, B, 10 Ga, P and Sb are most preferred. The amount of the impurity to be doped may be determined suitably depending on the desired electrical and optical characteristics.
As the substance containing such an impurity atom as the component (substance for introduction of impurity), it is preferably to select a compound which is gaseous under normal temperature and normal pressure, or gaseous at least under the activation conditions film and can be readily gasified by a suitable gasifying device.
Such compounds may include PH3, P2H4, PF3, PF5, PC13, AsH3, 20 AsF3, AsF5, AsC13, SbH3, SbF5, SiH3, BF3, BC13, BBr3, B2H6, 4 10' B5H9~ B5Hll' B6H10' B6H12, AlC13, etc. The compound5 containing impurity element may be used either singly or as a combination of two or more compounds.
The compound containing impurities as element 25 may be directly introduced under gaseous state into the film forming space, or alternatively activated previously in the activation space (A) or the activation space (B) or lZ9Z66Z
l a third activation space (C) before introduction into the film forming space.
In the present invention, during the film forming step (a), that is (A~ during film formation etching action is 5 applied on the growth surface of the deposited film at the same time, or (B) etching action is applied on the growth surface of the deposited film with film formation intermitted, whereby crystal growth can be effected pre-ferentially in a specific face direction to give a deposited 10 film with good crystallinity. The etching action in the case of the above (B) may be effected within the film forming space or alternatively in an etching space separate from the film forming space.
As the gaseous or readily gasifiable substance 15 for etching (E) having etching action on the deposited film containing silicon, there may be included single substances of halogen, halogen compounds or activated species (C) formed from these.
These substances (E) for etching may be 20 introduced under gaseous state into the space where etching action is applied to the deposited film, or alternatively in the case where the substance (E) is formed by the surface reaction on the surface of the deposited film of the above activated species (A) or the 25 above activated species tB), or formed from the chemical reaction between the activated species (A) and the activated species (B), etching action is applied on the 12g26~2 1 growth surface of the deposited film simultaneously with film formation.
For example, as an example in which the substance for etching is formed by the above surface reaction, the reaction between an activated species of halogen and hydrogen or a halogen and activated species of hydrogen occurs on the growth surface of the deposited film, and hydrogen halide ( HX ) is released from the growth surface of the deposited film and the hydrogen halide becomes the substance (E) for etching.
As the substance (E) having etching action in the present invention, there may be employed halogens such as F2, C12, gasified Br2, I2, etc., halogenated carbon such as CHF3, CF4, C2F6, CC14, CBrF3, CC12F2, 15 CC13F, CClF3 , C2C12F4, etc., halides including typically boron halides such as BC13 , BF3 and SF6, NF3, PF5, etc., and further radicals such as F*, Cl*, ions such as CF3 , CC13, from these gases. These can be used also as mixtures, and the etching characteristics can be also 20 controlled by adding 2' H2 and other gases in amounts which do not affect the film.
As the method for etching using the above sùbstance (E), etching and film formation may be repeated alternately by providing separately an etching space, 25 or they can be introduced under the state having etching activity into the film forming space to effect etching 1 action simultaneously with film formation, thereby giving the effect of limiting the growing direction of the crystalline film to accomplish the object of the present invention.
On the other hand, the dependency of growth speed upon face direction has been found during crystal growth of silicon or silicon-containing materials.
This may differ depending on the deposited film forming method or deposition conditions, but in the method of the present invention, the preferential order has been found to be (ll0) > (lll) ~ (l00).
By suitable selection of the kind of substance (E) for etching and etching condition under this condition, the condition with stronger orientability of (ll0) >~
(111) (100) can be realized. It is realized in the present invention to strengthen the above orientability and accelerate the growth speed, particularly by setting a portion for accelerating nucleation on the substrate. And, not only formation of polycrystalline deposited film with great grain size oriented only toward the (ll0) face is possible, but it is also possible to grow a single crystal by selecting the size, shape, interval, material, etc., of the nucleus.
In the present invention, the expression crystalline deposited film of course represents a polycrystalline and a single crystal film. The nucleation lZ9Z662 I surface provided on the substrate surface in the present invention are provided scatteringly in large number. As the property demanded for the nucleation surface, it may be mentioned that the active species (A) 5 in the vicinity of the substrate formed from compounds containing silicon and a halogen has a great coefficient of attachment. In order to enhance the coefficient of attachment, a material having a large coefficient of attachment may be employed or a surface structure for enhancing the coefficient of attachment may be formed. Coefficient of attachment generally refers to a guantity which is a measure for readiness in chemical adsorption to occur, and in the case of the present invention, physical adsorption and chemical adsorption including dissociation are also included.
As the surface structure enhancing the coefficient of attachment, those with surface unevenness of some 1000 A or less are preferred. As to the shape, those with shapes as regular as possible rather than random are preferred.
The material having a large coefficient of attachment may be selected from among insulating substances and semiconductive substances such as Si : N : H, Si3N4, A-Si : H, Si : N : O : H, Al2O3, SiO2, Ta2O5, etc., but particularly a compound containing Si-N is preferred. Also, a metal material may be sometimes employed. As mentioned above, the order ~ZS'Z662 1 of stronger orientability of crystal has been made as (110) ~ (111) ~ (100), but of course it is possible in the present invention to control the direction of oriented surface and the direction of the crystal 5 growth face depending on the conditions of deposition and nucleation.
The nucleation surface of the present invention does not have to be uniformly spread continuously over the whole substrate surface, but a film with regular 10 sized crystal grains and regular crystal axis directions may be obtained by locally providing the nucleation surface scatteringly while determining its area depending on the purposes.
Fig. 1 is a schematic sectional view illustrating the main part of an apparatus for forming a deposited film for embodying the present process.
In Fig. 1, numeral 101 is a deposition compartment where deposition of a silicon thin film is effected, and the deposition compartment 101 is connected to an exhausting system, not shown on the drawing, through a vent 106 to maintain the deposition compartment under a desired pressure. In the deposition compartment 101, an inlet pipe 102 for introducing a radical 107 containing Si and halogen as an activated speices (A), an inlet pipe 103 for introducing a hydrogen radical 107A as an activated species (8) and an inlet pipe 111 for introducing F2 gas 112 as a gaseous substance (E) I having etching action are enlarged to form action compartments 108, 108A and 113, respectively, and are narrowed at the outlet ends 109, 109A and 114, respectively. In the deposition compartment 101, a substrate support 104 is supported by rollers 110 and llOA so that the substrate support 104 can reciprocatingly moved in a direction perpendicular to the drawing surface, and the substrate 105 for deposition on which nucleation surface has been previously provided is supported on 10 the substrate support 104. The respective radicals and F2 gas discharged at the outlet ends 109, lO9A
and 114 are mixed together near the substrate in the deposition compartment 101 to undergo reaction there-between and form a deposited film on the substrate 105 while being etchsd.
The radicals containing silicon and halogen and the hydrogen radicals are formed from their starting material gases in heating furnaces or radical-forming sections in plasma chambers, etc., not shown in the 20 drawing, respectively, and then introduced into the action compartments 108 and 108A through the inlet pipes 102 and 103, respectively. The flow rates of the radicals are controlled by mass flow controllers provided at positions towards the gas sources from the heating furnaces or plasma chambers, respectively.
When the substrate 105 is longer in the direction perpendicular to the drawing surface, the substrate 1 105 is made to move by means of the rollers 110 and llOA in order to deposit a silicon thin film on the entire surface of the substrate.
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129Z6~2 I Example l In an apparatus shown in Fig. 2 having the apparatus in the part which has the same structure as shown in Fig. l, a glass substrate 205 was placed on a structure 5 holder in a structure pretreatment compartment 214, and exposed through a quartz window 215 to ArF excimer laser having a wavelength of 193 nm and a pulse width of 20 n sec after focussed to a laser spot having a spot size of about 10 ym through an optical system 10 at 8W /cm and 80 pulses, while keeping the glass substrate 205 at 250 C, and passing 50 sccm of Si2H6 under a pressure of 5 Torr as a reactive gas, whereby amorphous silicon films area 302 where formed at distances of l ,um (Fig. 3) on the glass state 205. Further, the glass substrate 205 is shown as 301 in Fig. 3.
The substrate 205A whose nucleation formation surface was thus prepared scatteringly on the surface in advance was transferred into a reaction compartment 213 form the nucleation compartment 214 to form a polycrystalline film on the said substrate 205A as follows.
First, SiF4 gas as a raw material gas for forming radicals containing silicon and halogen was introduced into a reaction furnace kept at 1,100 C, and decomposed, and then discharged into a reaction compartment 208 from an inlet pipe 202, while H2 gas was introduced into an inlet pipe 203. At this time, decomposed by supplying a microwave of 2.45 GHz at a power of 0.8 W/cm ~Z9Z6~Z
I to the inlet pipe 203 to form hydrogen radical and the said radicals were discharged into the reaction compartment 208. Furthermore, XeF2 as an etching gas was supplied towards the substrate 205A from an inlet pipe 211 at the same time. The substrate was kept at a temperature of 300 C. A ratio of flow rate (sccm) of XeF2 gas to flow rate (sccm) of SiF4 was changed to 5/100, 10/100, 15/100, 20/100, and 30/100, each kept under a pressure of 0.5 Torr for one hour to form films. As a result, films having the characterisitcs shown in Table 1 were deposited. Grain sizes were measured by a transmission type electron microscope.
Among the samples, the mobility values of sample No. 3 having the best mobility measurement values is shown in Table 2. For comparison, measurement values of sample R in which the polycrystalline Si film formed on a glass substrate having no treatment of formation of nucleation surface as sample No. 3 is shown in Table 2. It is evident from Table 2 that the present invention can 20 provide films of good characteristics, i.e. good orientation and less fluctuation.
Example 2 3 sccm of Si2H6 and 100 sccm of NH3 were used as reactive gases, but under a pressure of 10 Torr to 25 form amorphous silicon nitride films spotwise on the glass substrate, and then a polycrystalline film was deposited thereon in the same manner as Sample 3 in Example 1.
lZ9Z662 1 And, the result were evaluated as the same as in Example 1. The results are shown in Tables 2 and 3.
Example 3 In formation of the nucleation surface, except amorphous silicon nitride films were formed spotwise on the glass substrate with flowing 200 sccm of NH3 as a reactive gas, and under a pressure of 50 Torr, polycrystalline Si film was deposited on the glass substrate in the same conditions as Sample 3 in Example 1 and the characteristics were evalutated in a similar manner as Example 1. The results are shown in Table 3 (sample No. 3-1) Example 4 After amorphous silicon films were deposited on the glasssubstrate spotwise under the same conditions as in Example 1, then spotwise crystallized silicon films was further obtained by applying ArF excimer laser on the above-mentioned amorphous silicon film.
A polycrystalline Si film was deposited thereon at the same condition as in sample No. 3 in Example 1 and the characteristics were evaluated in the same manner as in Example 1 (sample 4-1). The results are shown in Tables 2 and 3.
Example 5 Except reactive etching gas F2 was used for forming nucleation surface to etch a glass substrate spotwise under a pressure of 5 Torr , the substrate ~Z9Z6~2 1 401 for formation of deposited film having the structure such as shown in Fig. 4 is formed. Using this substrate 401, the polycrystalline Si film was deposited and the characteristics thereof were evaluated in the same 5 manner as Example 1 (Sample 5-1). The results are shown in Tables 2 and 3.
Example 6 A glass plate 505 (#7059, made by Corning Glass Works) prebacked after spinner coating of polymethyl 10 methacrylate (P-MMA) as a positive type resist was placed in an electron beam irradiation apparatus as shown in Fig. 5, and then sublected to electron beam irradiation on the resist film as follows. Electrons emitted from an electron gun 501 were irradiated on the glass substrate. As an accelerated convergent electron beam through deflection electrodes 503a and 503b and control electrodes 502a and 502b. The electron beam at this time had 3 mA of a beam current at 5 ~eV of an acceleration voltage. The electron beam was irradiated 20 on the resist film of above-mentioned glass substrate 505 spotwise having a diameter of 0.1 jum at intervals of 0.1 ~um. There were 10 5 Torr of vacuum at this time. Thus, the substrate having a structure as shown in Fig. 6 for forming the deposited film (the glass substrate 505 is shown as 601 and the resist film prepared unevenness on the surface is shown lZ926~2 as 602) was prepared. I~he polycrystalline film was deposited on this substrate at the same condition as Sample No. 3 in Example 1 (sample 5-1). About this sample, the characteristics were evaluated in the same 5 manner as Example 1. The results are shown in Tables 2 and 3.
Example 7 An amourphous silicon thin film was formed on a glass substrate by RF glow discharge. Except setting 10 the laser pulse number for 150 and without using the reactive glass, local annealing was done by irradiating the laser on this amorphous silicon thin film on the glass substrate in the same manner as in Example 1, being crystallized locally. Then, a polycrystalline film 15 was deposited on the thus obtained substrate for formation of the deposited film under the same conditions as in Sample No. 3 (sample 7-1). Characteristics of the sample was obtained in the same manner as in Example 1. The results are shown in Tables 2 and 3.
20 Example 8 A film consisting of 11 diacetylene layers was deposited on a glass substrate (#7059, made by corning Glass Works) according to LB method in the following manner. That is, a glass substrate was 25 at first washed with ultrapure water to remove oily matters therefrom, and then dipped into water. Then, a few drops of a solution of diacetylene in chloroform I a~ a concentration of 5 x 10 3 mol/l was added thereto, and after a given pressure was applied to the liquid surface. Then, the glass substrate was vertically reciprocated at a speed of 1 cm/min while maintaining 5 the pressure to deposit a film consisting of 11 layers.
Then, the film was exposed to a focussed UV light (254 nm) at a power of 10 mWJcm2 to effect local polymerization.
So, characteristics for formation of deposited film formed.
Using this substrate, a polycrystalline Si was prepared in the same manner as in Sample No. 3 (Sample No. 8-1). The characteristics were evaluated in the same as in Example 1. The results are shown in Tables 2 and 3.
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Field of the Invention This invention relates to a process suitable for forming a functional deposited film containing silicon, particularly a polycrystalline silicon deposited film for use in semiconductor devices, photosensitive device, line sensors for image input, image pick-up devices, etc.
Related Background Art Heretofore, a process for forming a polycrystalline or monocrystalline semiconductor layer composed of coarse grains by exposing a polycrystalline or amorphous semiconductor layer on an insulating substrate to an energy beam has been proposed as prior art. For example, a polycrystalline or monocrystalline silicon layer composed of coarse grains can be formed by coating a silicon substrate with an insulating film of SiO2 or SiN, depositing a polycrystalline layer thereon by CVD in reduced pressure or normal pressure or by plasma CVD, and subjecting the polycrystalline layer to annealing by irradiation of a continuous laser beam or electron beam. However, it is difficult to control crystal grain size, crystal grain size distribution, crystal lZ926~j2 1 grain site, etc. of polycrystalline silicon or crystal face orientation according to the piror art process.
Therefore, in semiconductor devices where semiconductor elements are formed on a semiconductor substrate 5 as described above, fluctuation and reliability in their characteristics have been thus problems.
According to another prior art process, a polycrystalline layer composed of coarse grains or a monocrystalline layer is formed by forming regular grooves tgratings) on an insulating film surface, depositing a polycrystalline or amorphous silicon layer thereon, and annealing the layer (graphoepitaxial process).
However, this process has a poor reproducibility and the crystal face orientation cannot be completely controlled. Thus, a novel process for, depositing a film free from these problems has been desired.
SUMMARY OF THE INVENTION
The primary object of the present invention is to provide a novel process for forming a polycrystalline silicon deposited film free from the problems of the prior art processes as described above and not based on the conventional process.
Another object of the present invention is to solve the said problems and provide a process for forming a deposited film by which a polycrystalline film of good quality and uniform crystal face iZ9Z6~Z
I orientation can be obtained.
Still another object of the present invention is to provide a process for forming a polycrystalline deposited film, which comprises selectively irradiating a substrate with an energy beam obtained by previously conversing energy such as an electromagnetic wave such as light, microwave, etc., and an electron beam etc.
to limit the sites of crystal nucleation on the substrate, and effecting film formation while controlling crystal grain size of polycrystal.
Yet another object of the present invention is to provide a process for forming a polycrystalline deposited film which is suitable for enlargement of the area of the film and can easily accomplish improvement of productivity and bulk production of the film, while attempting to improve the characteristics of the film formed, the film forming speed and reproducibility and also to uniformize film quality.
According to the present invention, there is provided a process for forming a deposited film comprising the steps of:
(a) preparing a substrate for deposited film formation by selectively irradiating the surface of a base member with an energy beam of an electro-magnetic wave or electron beam through atmosphereof a reactive gas or a gas having etching action to provide regions where crystal nuclei are selectively 12~Z6~2 I formed scatteringly on the surface;
(b) forming a deposited film on said substrate by introducing an activated species (A) formed by decomposition of a compound (SX) containing silicon and 5 a halogen and an activated species (B) formed from a chemical substance (B) for film formation which is chemically mutually reactive with said activated species (A) separately from each other into a film forming space in which said substrate is previously arranged to effect chemical reaction therebetween; and (c) introducing into said film forming space during the film forming step (b) a gaseous substance (E) having etching action on the deposited film to be formed or a gaseous substance (E2) capable of forming the gaseous substance (E) and exposing the deposited film growth surface to the gaseous substance (E) to apply etching action on the deposited film growth surface, thereby effecting preferentially crystal growth in a specific face direction.
~RIEF DESCRIPTION OF THE DRAWINGS
Figs. 1 and 2 are each schematic views illustrating the main part of a deposited film forming device for embodying the process of the present invention.
129Z66;~
I Figs. 3, 4 and 6 are each schematic views illustrating the substrate for deposited film formation used in Examples.
Fig. 5 is a schematic illustration of the main part of the electron beam irradiating device which is a substrate preparing device used in Example.
DESCRIPTION OF THE PREFERRED EMBODIMENT
At first, a procedure for selectively providing crystal nucleation regions (nucleation surface) on a substrate beforehand will be described below, and then a procedure capable of controlling the crystal face direction (orientation) and polycrystal grain size using the substrate will be described.
Crystal nucleation regions can be selectively formed on a substrate, for example, i) by locally and spotwise irradiating the substrate with an energy beam of a convergent electromagnetic wave such as light, microwave, etc. or an electron beam, thereby locally forming a deposited film on the substrate, or ii) by locally etching the substrate, thereby making the substrate surface irregular, or iii) by locally and spotwise irradiating the substrate with an energy beam, thereby crystallizing parts of the substrate surface or iv) effecting isomerization treatment of the substrate surface, thereby changing the adsorption characteristics or chemical activity of the substrate 12~Z66Z
I surface; that is, providing locally a surface-energetic or physical localization on the substrate. Specifically, as the above process (i), there is mentioned, for example, a process comprising irradiating a substrate 5 locally and spotwise through reactive gases with an energy beam obtained by converging an electromagnetic wave such as light, microwave, etc. or an electron beam to locally deposit a deposit film onto the substrate.
As the above process (ii), there is mentioned, for example, a process in which the substrate surface is locally made irregular by using a reactive etching gas in place of reactive gases, or a process in which a positive type resist is applied to the substrate and the substrate is exposed locally to an energy beam to make the substrate surface irregular. As the above processes (iii) and (iv), there is mentioned, for example, a process in which an amorphous thin film is deposited on a substrate by a known method, for example, by RF glow discharge, vacuum vapor deposition, sputtering or light CVD
beforehand, and then the substrate is exposed locally to an energy beam to effect crystallization or isomerization, or a process in which a thin film of an organic compound is deposited on a substrate by interfacial adsorption such as by monomolecular layer build-up (LB method), gaseous phase adsorption, liquid phase adsorption, etc. or by electrolytic polymerization, vapor deposition or sputtering, and then the substrate ~2~2t;t`2 1 is exposed locally to the energy beam to effect isomerization or crystallization. Or a substrate of polymeric material is exposed locally to an energy beam to effect isomerization to form nucleation regions.
Next, process for forming a film while controll-ing thP orientation, grain size and grain size distribution of the crystal by using a substrate having crystal nucleation regions provided selectively thereon according to the above processes will be described below.
In the present invention, as a first step, a substrate having a nucleation surface provided , _ /
/
lZ9Z6~Z
I selectively on the surface thereof is previously arranged in a film forming space for formation of a deposited film [Step (a)).
Next, an activated species (A) formed by decomposition of a compound (SX) containing silicon and a halogen and an activated species (B) formed from a chemical substance (B) for film formation which is chemically mutually reactive with the activated species (A) are introduced separately from each other into the film forming space to effect chemical reaction therebetween, thereby forming a deposited film on the substrate [Film forming Step (b)).
During the film forming step (b), a gaseous substance (E) having etching action on the deposited film to be formed or a gaseous substance (E2) capable of forming the gaseous substance (E) are introduced into the film forming space and the deposited film growth surface is exposed to the gaseous substance (E) to apply etching action on the deposited film growth surface, thereby effecting preferentially crystal growth in a specific face direction ~Step (c)~.
As described above, by providing the above steps (a)- (c) film formation can be effected while 25 desirably controlling the orientation, crystal grain size and grain size distribution and exhibiting the 129Z6~2 I technical advantage as described below.
The technical advantage accomplished according to the process of the present invention is that the deposited film formed in the copresence of an active 5 species (A) formed by decomposition of a compound containing silicon and halogen and another species (B) formed from a chemical substance for forming a film in a film-forming space in place of generating a plasma is insusceptible to adverse effects of the plasma.
Another advantage of the present invention is that a stable CVD process can be provided since the atmosphere temperature of the film forming space and the substrate temperature can be desirably controlled.
Still another advantage of the present process is accomplished by use of an active species previously activated in a different activation space from the film-forming space. That is the film-forming speed can be made drastically higher and the substrate temperature for forming a deposit film can be made much lower than the conventional CVD process while film characteristic of good quality can be obtained. Furthermore, there can be mentioned the advantage that a crystalline film can be formed having a specific crystal face orientation, that is, a film of good quality with a specific orientation of high degree and uniform grain size by the I etching effect of the gaseous material (E) having etching action.
The compound (SX) containing silicon and halogen to be introduced into the activation space (A) in the present invention, includes for example, linear or cyclic silane compounds, part or whole of whose hydrogen atoms are substituted with halogen atoms, are used. Specifically, linear silicon halides represented by SiuY2u+2, where u is an integer of 1 or more, Y is at least one element selected from F, Cl, Br and I, cyclic silicon halides represented by SivY2v, where v is an integer of 3 or more and Y has the same meaning as defined above, and linear or cyclic compounds represented by SiUHxYy, where u and Y have the same meaning as defined above and x + y = 2u or 2u + 2. More specifically, gaseous or reading gasifying compounds such as SiF4, (SiF2)5, 2 6 2)4' Si2F6, Si3F8, SiHF3, SiH2F SiCl (SiC12)5, SiBr4, (SiBr2)5, Si2C16, Si2Br6, SiHC13, 20 SiH3Cl, SiH2C12, SiHBr3, SiHC13, Si2C13F3, etc. can be enumerated.
In order to form an active species (A), silicon simple substance and other silicon compounds, hydrogen, halogen compounds (for example, F2 gas, C12 gas, gasified Br2,I2, etc.), etc. can be used together, if necessary, in addition to the compound containing silicon and halogen (SX).
6~;2 I In the present invention, the active species (A) is formed in the activation space (A) by an activation energy such as an elec~ric energy, for example, microwave, RF, low frequency wave, DC, etc., a thermal energy such as heater heating, infrared heating, etc., a photo energy, etc. in view of various given conditions and apparatuses.
As the chemical substance for forming a film to form the active species ( B ) in the activation space 10 (B) hydrogen gas and/or a halogen compound (for example, F2 gas, C12 gas, gasified Br2,I2, etc.) can be advantageously used. In addition to the chemical substance for forming a film, an inert gas such as helium, argon, neon, etc. can be used. When a plurality of these chemical substances for forming a film are used, they can be introduced in a gaseous state into the activation space (B) after mixing them in advance, or these chemical substances for forming a film can be separately introduced into the activation space 20 (B) from their independent supply sources, or introduced into the respective, independent activation spaces to make individual activations.
In the present invention, a mixing ratio of the active species (A) to the active species (B) to 25 be introduced into the film forming space is determined, as desired, in view of the film-forming conditions, lZgZ662 I kinds o the active species, etc., and is preferably 10:1 to 1:10 (introducing flow rate ratio), more preferably 8:2 to 4:6.
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1 Also, the deposited film formed according to the present inven~ion can be doped with the so-called impurity element used in the field of semiconductor during or after film formation. As the impurity element to be used, there may be employed, as p-type impurity, an element belonging to the group IIIA of the periodic table such as B, Al, Ga, In, Tl, etc. and, as n-type purity, an element belonging to the group VA of the periodic table such as P, As, Sb, Bi, etc. as suitable ones. Particularly, B, 10 Ga, P and Sb are most preferred. The amount of the impurity to be doped may be determined suitably depending on the desired electrical and optical characteristics.
As the substance containing such an impurity atom as the component (substance for introduction of impurity), it is preferably to select a compound which is gaseous under normal temperature and normal pressure, or gaseous at least under the activation conditions film and can be readily gasified by a suitable gasifying device.
Such compounds may include PH3, P2H4, PF3, PF5, PC13, AsH3, 20 AsF3, AsF5, AsC13, SbH3, SbF5, SiH3, BF3, BC13, BBr3, B2H6, 4 10' B5H9~ B5Hll' B6H10' B6H12, AlC13, etc. The compound5 containing impurity element may be used either singly or as a combination of two or more compounds.
The compound containing impurities as element 25 may be directly introduced under gaseous state into the film forming space, or alternatively activated previously in the activation space (A) or the activation space (B) or lZ9Z66Z
l a third activation space (C) before introduction into the film forming space.
In the present invention, during the film forming step (a), that is (A~ during film formation etching action is 5 applied on the growth surface of the deposited film at the same time, or (B) etching action is applied on the growth surface of the deposited film with film formation intermitted, whereby crystal growth can be effected pre-ferentially in a specific face direction to give a deposited 10 film with good crystallinity. The etching action in the case of the above (B) may be effected within the film forming space or alternatively in an etching space separate from the film forming space.
As the gaseous or readily gasifiable substance 15 for etching (E) having etching action on the deposited film containing silicon, there may be included single substances of halogen, halogen compounds or activated species (C) formed from these.
These substances (E) for etching may be 20 introduced under gaseous state into the space where etching action is applied to the deposited film, or alternatively in the case where the substance (E) is formed by the surface reaction on the surface of the deposited film of the above activated species (A) or the 25 above activated species tB), or formed from the chemical reaction between the activated species (A) and the activated species (B), etching action is applied on the 12g26~2 1 growth surface of the deposited film simultaneously with film formation.
For example, as an example in which the substance for etching is formed by the above surface reaction, the reaction between an activated species of halogen and hydrogen or a halogen and activated species of hydrogen occurs on the growth surface of the deposited film, and hydrogen halide ( HX ) is released from the growth surface of the deposited film and the hydrogen halide becomes the substance (E) for etching.
As the substance (E) having etching action in the present invention, there may be employed halogens such as F2, C12, gasified Br2, I2, etc., halogenated carbon such as CHF3, CF4, C2F6, CC14, CBrF3, CC12F2, 15 CC13F, CClF3 , C2C12F4, etc., halides including typically boron halides such as BC13 , BF3 and SF6, NF3, PF5, etc., and further radicals such as F*, Cl*, ions such as CF3 , CC13, from these gases. These can be used also as mixtures, and the etching characteristics can be also 20 controlled by adding 2' H2 and other gases in amounts which do not affect the film.
As the method for etching using the above sùbstance (E), etching and film formation may be repeated alternately by providing separately an etching space, 25 or they can be introduced under the state having etching activity into the film forming space to effect etching 1 action simultaneously with film formation, thereby giving the effect of limiting the growing direction of the crystalline film to accomplish the object of the present invention.
On the other hand, the dependency of growth speed upon face direction has been found during crystal growth of silicon or silicon-containing materials.
This may differ depending on the deposited film forming method or deposition conditions, but in the method of the present invention, the preferential order has been found to be (ll0) > (lll) ~ (l00).
By suitable selection of the kind of substance (E) for etching and etching condition under this condition, the condition with stronger orientability of (ll0) >~
(111) (100) can be realized. It is realized in the present invention to strengthen the above orientability and accelerate the growth speed, particularly by setting a portion for accelerating nucleation on the substrate. And, not only formation of polycrystalline deposited film with great grain size oriented only toward the (ll0) face is possible, but it is also possible to grow a single crystal by selecting the size, shape, interval, material, etc., of the nucleus.
In the present invention, the expression crystalline deposited film of course represents a polycrystalline and a single crystal film. The nucleation lZ9Z662 I surface provided on the substrate surface in the present invention are provided scatteringly in large number. As the property demanded for the nucleation surface, it may be mentioned that the active species (A) 5 in the vicinity of the substrate formed from compounds containing silicon and a halogen has a great coefficient of attachment. In order to enhance the coefficient of attachment, a material having a large coefficient of attachment may be employed or a surface structure for enhancing the coefficient of attachment may be formed. Coefficient of attachment generally refers to a guantity which is a measure for readiness in chemical adsorption to occur, and in the case of the present invention, physical adsorption and chemical adsorption including dissociation are also included.
As the surface structure enhancing the coefficient of attachment, those with surface unevenness of some 1000 A or less are preferred. As to the shape, those with shapes as regular as possible rather than random are preferred.
The material having a large coefficient of attachment may be selected from among insulating substances and semiconductive substances such as Si : N : H, Si3N4, A-Si : H, Si : N : O : H, Al2O3, SiO2, Ta2O5, etc., but particularly a compound containing Si-N is preferred. Also, a metal material may be sometimes employed. As mentioned above, the order ~ZS'Z662 1 of stronger orientability of crystal has been made as (110) ~ (111) ~ (100), but of course it is possible in the present invention to control the direction of oriented surface and the direction of the crystal 5 growth face depending on the conditions of deposition and nucleation.
The nucleation surface of the present invention does not have to be uniformly spread continuously over the whole substrate surface, but a film with regular 10 sized crystal grains and regular crystal axis directions may be obtained by locally providing the nucleation surface scatteringly while determining its area depending on the purposes.
Fig. 1 is a schematic sectional view illustrating the main part of an apparatus for forming a deposited film for embodying the present process.
In Fig. 1, numeral 101 is a deposition compartment where deposition of a silicon thin film is effected, and the deposition compartment 101 is connected to an exhausting system, not shown on the drawing, through a vent 106 to maintain the deposition compartment under a desired pressure. In the deposition compartment 101, an inlet pipe 102 for introducing a radical 107 containing Si and halogen as an activated speices (A), an inlet pipe 103 for introducing a hydrogen radical 107A as an activated species (8) and an inlet pipe 111 for introducing F2 gas 112 as a gaseous substance (E) I having etching action are enlarged to form action compartments 108, 108A and 113, respectively, and are narrowed at the outlet ends 109, 109A and 114, respectively. In the deposition compartment 101, a substrate support 104 is supported by rollers 110 and llOA so that the substrate support 104 can reciprocatingly moved in a direction perpendicular to the drawing surface, and the substrate 105 for deposition on which nucleation surface has been previously provided is supported on 10 the substrate support 104. The respective radicals and F2 gas discharged at the outlet ends 109, lO9A
and 114 are mixed together near the substrate in the deposition compartment 101 to undergo reaction there-between and form a deposited film on the substrate 105 while being etchsd.
The radicals containing silicon and halogen and the hydrogen radicals are formed from their starting material gases in heating furnaces or radical-forming sections in plasma chambers, etc., not shown in the 20 drawing, respectively, and then introduced into the action compartments 108 and 108A through the inlet pipes 102 and 103, respectively. The flow rates of the radicals are controlled by mass flow controllers provided at positions towards the gas sources from the heating furnaces or plasma chambers, respectively.
When the substrate 105 is longer in the direction perpendicular to the drawing surface, the substrate 1 105 is made to move by means of the rollers 110 and llOA in order to deposit a silicon thin film on the entire surface of the substrate.
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129Z6~2 I Example l In an apparatus shown in Fig. 2 having the apparatus in the part which has the same structure as shown in Fig. l, a glass substrate 205 was placed on a structure 5 holder in a structure pretreatment compartment 214, and exposed through a quartz window 215 to ArF excimer laser having a wavelength of 193 nm and a pulse width of 20 n sec after focussed to a laser spot having a spot size of about 10 ym through an optical system 10 at 8W /cm and 80 pulses, while keeping the glass substrate 205 at 250 C, and passing 50 sccm of Si2H6 under a pressure of 5 Torr as a reactive gas, whereby amorphous silicon films area 302 where formed at distances of l ,um (Fig. 3) on the glass state 205. Further, the glass substrate 205 is shown as 301 in Fig. 3.
The substrate 205A whose nucleation formation surface was thus prepared scatteringly on the surface in advance was transferred into a reaction compartment 213 form the nucleation compartment 214 to form a polycrystalline film on the said substrate 205A as follows.
First, SiF4 gas as a raw material gas for forming radicals containing silicon and halogen was introduced into a reaction furnace kept at 1,100 C, and decomposed, and then discharged into a reaction compartment 208 from an inlet pipe 202, while H2 gas was introduced into an inlet pipe 203. At this time, decomposed by supplying a microwave of 2.45 GHz at a power of 0.8 W/cm ~Z9Z6~Z
I to the inlet pipe 203 to form hydrogen radical and the said radicals were discharged into the reaction compartment 208. Furthermore, XeF2 as an etching gas was supplied towards the substrate 205A from an inlet pipe 211 at the same time. The substrate was kept at a temperature of 300 C. A ratio of flow rate (sccm) of XeF2 gas to flow rate (sccm) of SiF4 was changed to 5/100, 10/100, 15/100, 20/100, and 30/100, each kept under a pressure of 0.5 Torr for one hour to form films. As a result, films having the characterisitcs shown in Table 1 were deposited. Grain sizes were measured by a transmission type electron microscope.
Among the samples, the mobility values of sample No. 3 having the best mobility measurement values is shown in Table 2. For comparison, measurement values of sample R in which the polycrystalline Si film formed on a glass substrate having no treatment of formation of nucleation surface as sample No. 3 is shown in Table 2. It is evident from Table 2 that the present invention can 20 provide films of good characteristics, i.e. good orientation and less fluctuation.
Example 2 3 sccm of Si2H6 and 100 sccm of NH3 were used as reactive gases, but under a pressure of 10 Torr to 25 form amorphous silicon nitride films spotwise on the glass substrate, and then a polycrystalline film was deposited thereon in the same manner as Sample 3 in Example 1.
lZ9Z662 1 And, the result were evaluated as the same as in Example 1. The results are shown in Tables 2 and 3.
Example 3 In formation of the nucleation surface, except amorphous silicon nitride films were formed spotwise on the glass substrate with flowing 200 sccm of NH3 as a reactive gas, and under a pressure of 50 Torr, polycrystalline Si film was deposited on the glass substrate in the same conditions as Sample 3 in Example 1 and the characteristics were evalutated in a similar manner as Example 1. The results are shown in Table 3 (sample No. 3-1) Example 4 After amorphous silicon films were deposited on the glasssubstrate spotwise under the same conditions as in Example 1, then spotwise crystallized silicon films was further obtained by applying ArF excimer laser on the above-mentioned amorphous silicon film.
A polycrystalline Si film was deposited thereon at the same condition as in sample No. 3 in Example 1 and the characteristics were evaluated in the same manner as in Example 1 (sample 4-1). The results are shown in Tables 2 and 3.
Example 5 Except reactive etching gas F2 was used for forming nucleation surface to etch a glass substrate spotwise under a pressure of 5 Torr , the substrate ~Z9Z6~2 1 401 for formation of deposited film having the structure such as shown in Fig. 4 is formed. Using this substrate 401, the polycrystalline Si film was deposited and the characteristics thereof were evaluated in the same 5 manner as Example 1 (Sample 5-1). The results are shown in Tables 2 and 3.
Example 6 A glass plate 505 (#7059, made by Corning Glass Works) prebacked after spinner coating of polymethyl 10 methacrylate (P-MMA) as a positive type resist was placed in an electron beam irradiation apparatus as shown in Fig. 5, and then sublected to electron beam irradiation on the resist film as follows. Electrons emitted from an electron gun 501 were irradiated on the glass substrate. As an accelerated convergent electron beam through deflection electrodes 503a and 503b and control electrodes 502a and 502b. The electron beam at this time had 3 mA of a beam current at 5 ~eV of an acceleration voltage. The electron beam was irradiated 20 on the resist film of above-mentioned glass substrate 505 spotwise having a diameter of 0.1 jum at intervals of 0.1 ~um. There were 10 5 Torr of vacuum at this time. Thus, the substrate having a structure as shown in Fig. 6 for forming the deposited film (the glass substrate 505 is shown as 601 and the resist film prepared unevenness on the surface is shown lZ926~2 as 602) was prepared. I~he polycrystalline film was deposited on this substrate at the same condition as Sample No. 3 in Example 1 (sample 5-1). About this sample, the characteristics were evaluated in the same 5 manner as Example 1. The results are shown in Tables 2 and 3.
Example 7 An amourphous silicon thin film was formed on a glass substrate by RF glow discharge. Except setting 10 the laser pulse number for 150 and without using the reactive glass, local annealing was done by irradiating the laser on this amorphous silicon thin film on the glass substrate in the same manner as in Example 1, being crystallized locally. Then, a polycrystalline film 15 was deposited on the thus obtained substrate for formation of the deposited film under the same conditions as in Sample No. 3 (sample 7-1). Characteristics of the sample was obtained in the same manner as in Example 1. The results are shown in Tables 2 and 3.
20 Example 8 A film consisting of 11 diacetylene layers was deposited on a glass substrate (#7059, made by corning Glass Works) according to LB method in the following manner. That is, a glass substrate was 25 at first washed with ultrapure water to remove oily matters therefrom, and then dipped into water. Then, a few drops of a solution of diacetylene in chloroform I a~ a concentration of 5 x 10 3 mol/l was added thereto, and after a given pressure was applied to the liquid surface. Then, the glass substrate was vertically reciprocated at a speed of 1 cm/min while maintaining 5 the pressure to deposit a film consisting of 11 layers.
Then, the film was exposed to a focussed UV light (254 nm) at a power of 10 mWJcm2 to effect local polymerization.
So, characteristics for formation of deposited film formed.
Using this substrate, a polycrystalline Si was prepared in the same manner as in Sample No. 3 (Sample No. 8-1). The characteristics were evaluated in the same as in Example 1. The results are shown in Tables 2 and 3.
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Claims (9)
1. A process for forming a deposited film comprising the steps of:
(a) preparing a substrate for deposited film formation by selectively irradiating the surface of a base member with an energy beam of an electromagnetic wave or electron beam through atmosphere of a reactive gas or a gas having etching action to provide regions where crystal nuclei are selectively formed scatteringly on the surface;
(b) forming a deposited film on said substrate by introducing an activated species (A) formed by decomposition of a compound (SX) containing silicon and a halogen and an activated species (B) formed from a chemical substance (B) for film formation which is chemically mutually reactive with said activated species (A) separately from each other into a film forming space in which said substrate is previously arranged to effect chemical reaction therebetween; and (c) introducing into said film forming space during the film forming step (b) a gaseous substance (E) having etching action on the deposited film to be formed or a gaseous substance (E2) capable of forming the gaseous substance (E) and exposing the deposited film growth surface to the gaseous substance (E) to apply etching action on the deposited film growth surface, thereby effecting preferentially crystal growth in a specific face direction.
(a) preparing a substrate for deposited film formation by selectively irradiating the surface of a base member with an energy beam of an electromagnetic wave or electron beam through atmosphere of a reactive gas or a gas having etching action to provide regions where crystal nuclei are selectively formed scatteringly on the surface;
(b) forming a deposited film on said substrate by introducing an activated species (A) formed by decomposition of a compound (SX) containing silicon and a halogen and an activated species (B) formed from a chemical substance (B) for film formation which is chemically mutually reactive with said activated species (A) separately from each other into a film forming space in which said substrate is previously arranged to effect chemical reaction therebetween; and (c) introducing into said film forming space during the film forming step (b) a gaseous substance (E) having etching action on the deposited film to be formed or a gaseous substance (E2) capable of forming the gaseous substance (E) and exposing the deposited film growth surface to the gaseous substance (E) to apply etching action on the deposited film growth surface, thereby effecting preferentially crystal growth in a specific face direction.
2. A process for forming deposited film according to Claim 1, wherein said compound (SX) is a chain halogenated silicon represented by the formula SiUY2U+2 (wherein u is an integer of 1 or more, Y is at least one element selected from F, Cl, Br and I).
3. A process for forming deposited film according to Claim 1, wherein said compound (SX) is a chain or cyclic halogenated silicon represented by the formula SiUHxYy (wherein u, x, y are integers of 1 or more, x + y = 2u or x + y = 2u + 2, and Y is at least one element selected from F, Cl, Br and I).
4. A process for forming deposited film according to Claim 1, wherein either one of hydrogen and halogen is used in addition to said compound (SX) during decomposition of said compound (SX).
5. A process for forming deposited film according to Claim 1, wherein said chemical substance (B) for film formation is either one of hydrogen gas and halogen gas.
6. A process for forming deposited film according to Claim 1, wherein the flow rate ratio of said active species (A) and said active species (B) when introduced into the film-forming space is 10 : 1 to 1 : 10.
7. A process for forming deposited film according to Claim 1, wherein a compound containing an impurity element as the component is permitted to coexist with said compound (SX) during formation of said activated species (A).
8. A process for forming deposited film according to Claim 1, wherein a compound containing an impurity element as the component is permitted to coexist with said chemical substance (B) for film formation during formation of said activated species (B).
9. A process for forming deposited film according to Claim 1, wherein an activated species (D) formed from a compound containing an impurity element as the component is introduced into said film-forming space.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61086826A JPH0639703B2 (en) | 1986-04-15 | 1986-04-15 | Deposited film formation method |
| JP086826/1986 | 1986-04-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1292662C true CA1292662C (en) | 1991-12-03 |
Family
ID=13897615
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000534808A Expired - Lifetime CA1292662C (en) | 1986-04-15 | 1987-04-15 | Process for forming deposited film |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US4942058A (en) |
| EP (1) | EP0242207B1 (en) |
| JP (1) | JPH0639703B2 (en) |
| AT (1) | ATE86794T1 (en) |
| AU (1) | AU598247B2 (en) |
| CA (1) | CA1292662C (en) |
| DE (1) | DE3784541T2 (en) |
| ES (1) | ES2054666T3 (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0241311B1 (en) * | 1986-04-11 | 1993-03-17 | Canon Kabushiki Kaisha | Process for forming deposited film |
| EP0241317B1 (en) * | 1986-04-11 | 1993-03-10 | Canon Kabushiki Kaisha | Process for forming deposited film |
| JPH0639702B2 (en) * | 1986-04-14 | 1994-05-25 | キヤノン株式会社 | Deposited film formation method |
| DE3786364T2 (en) * | 1986-04-14 | 1993-11-18 | Canon Kk | Process for producing a deposited layer. |
| JP2768685B2 (en) * | 1988-03-28 | 1998-06-25 | 株式会社東芝 | Semiconductor device manufacturing method and device |
| JPH0244786A (en) * | 1988-08-05 | 1990-02-14 | Canon Inc | Manufacture of josephson element |
| JPH02225399A (en) * | 1988-11-11 | 1990-09-07 | Fujitsu Ltd | Method for epitaxial growth and apparatus therefor |
| JPH02208293A (en) * | 1989-02-08 | 1990-08-17 | Kanazawa Univ | Production of polycrystalline silicon film |
| JPH02258689A (en) * | 1989-03-31 | 1990-10-19 | Canon Inc | Method for forming crystalline thin film |
| JP3535241B2 (en) * | 1994-11-18 | 2004-06-07 | 株式会社半導体エネルギー研究所 | Semiconductor device and manufacturing method thereof |
| JP3469337B2 (en) | 1994-12-16 | 2003-11-25 | 株式会社半導体エネルギー研究所 | Method for manufacturing semiconductor device |
| US6652922B1 (en) * | 1995-06-15 | 2003-11-25 | Alliedsignal Inc. | Electron-beam processed films for microelectronics structures |
| US6027960A (en) | 1995-10-25 | 2000-02-22 | Semiconductor Energy Laboratory Co., Ltd. | Laser annealing method and laser annealing device |
| US6783627B1 (en) | 2000-01-20 | 2004-08-31 | Kokusai Semiconductor Equipment Corporation | Reactor with remote plasma system and method of processing a semiconductor substrate |
| US6521961B1 (en) * | 2000-04-28 | 2003-02-18 | Motorola, Inc. | Semiconductor device using a barrier layer between the gate electrode and substrate and method therefor |
| US7087504B2 (en) * | 2001-05-18 | 2006-08-08 | Semiconductor Energy Laboratory Co., Ltd. | Method of manufacturing a semiconductor device by irradiating with a laser beam |
| US6780786B2 (en) * | 2001-11-26 | 2004-08-24 | The Regents Of The University Of California | Method for producing a porous silicon film |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2151346C3 (en) * | 1971-10-15 | 1981-04-09 | Deutsche Itt Industries Gmbh, 7800 Freiburg | Method for producing a semiconductor layer consisting of single crystal layer parts and polycrystal layer parts on a single crystal body |
| JPS5587425A (en) * | 1978-12-26 | 1980-07-02 | Tohoku Metal Ind Ltd | Doping method for epitaxial layer of semiconductor |
| JPS5767938A (en) * | 1980-10-16 | 1982-04-24 | Canon Inc | Production of photoconductive member |
| DE3107260A1 (en) * | 1981-02-26 | 1982-09-09 | Siemens AG, 1000 Berlin und 8000 München | Process and appliance for depositing semiconductor material, especially silicon |
| US4608117A (en) * | 1982-06-01 | 1986-08-26 | Massachusetts Institute Of Technology | Maskless growth of patterned films |
| US4522662A (en) * | 1983-08-12 | 1985-06-11 | Hewlett-Packard Company | CVD lateral epitaxial growth of silicon over insulators |
| JPS6126774A (en) * | 1984-07-16 | 1986-02-06 | Canon Inc | Apparatus for forming amorphous silicon film |
| FR2580673B1 (en) * | 1985-04-19 | 1987-09-25 | Haond Michel | METHOD FOR MANUFACTURING ON AN INSULATING SUPPORT OF A SINGLE-CRYSTAL, LOCAL-DEFECT SILICON FILM |
| US4791071A (en) * | 1986-02-20 | 1988-12-13 | Texas Instruments Incorporated | Dual dielectric gate system comprising silicon dioxide and amorphous silicon |
| EP0241311B1 (en) * | 1986-04-11 | 1993-03-17 | Canon Kabushiki Kaisha | Process for forming deposited film |
| EP0241317B1 (en) * | 1986-04-11 | 1993-03-10 | Canon Kabushiki Kaisha | Process for forming deposited film |
| JPH0639702B2 (en) * | 1986-04-14 | 1994-05-25 | キヤノン株式会社 | Deposited film formation method |
| DE3786364T2 (en) * | 1986-04-14 | 1993-11-18 | Canon Kk | Process for producing a deposited layer. |
-
1986
- 1986-04-15 JP JP61086826A patent/JPH0639703B2/en not_active Expired - Lifetime
-
1987
- 1987-04-14 AU AU71515/87A patent/AU598247B2/en not_active Ceased
- 1987-04-15 AT AT87303341T patent/ATE86794T1/en active
- 1987-04-15 DE DE87303341T patent/DE3784541T2/en not_active Expired - Fee Related
- 1987-04-15 EP EP87303341A patent/EP0242207B1/en not_active Expired - Lifetime
- 1987-04-15 ES ES87303341T patent/ES2054666T3/en not_active Expired - Lifetime
- 1987-04-15 CA CA000534808A patent/CA1292662C/en not_active Expired - Lifetime
-
1989
- 1989-06-08 US US07/363,309 patent/US4942058A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0639703B2 (en) | 1994-05-25 |
| EP0242207A3 (en) | 1988-09-07 |
| ATE86794T1 (en) | 1993-03-15 |
| JPS62243768A (en) | 1987-10-24 |
| ES2054666T3 (en) | 1994-08-16 |
| DE3784541D1 (en) | 1993-04-15 |
| EP0242207B1 (en) | 1993-03-10 |
| EP0242207A2 (en) | 1987-10-21 |
| AU7151587A (en) | 1987-10-22 |
| DE3784541T2 (en) | 1993-09-30 |
| AU598247B2 (en) | 1990-06-21 |
| US4942058A (en) | 1990-07-17 |
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