CA2023684A1 - Chemical vapor deposition apparatus for forming thin film - Google Patents
Chemical vapor deposition apparatus for forming thin filmInfo
- Publication number
- CA2023684A1 CA2023684A1 CA002023684A CA2023684A CA2023684A1 CA 2023684 A1 CA2023684 A1 CA 2023684A1 CA 002023684 A CA002023684 A CA 002023684A CA 2023684 A CA2023684 A CA 2023684A CA 2023684 A1 CA2023684 A1 CA 2023684A1
- Authority
- CA
- Canada
- Prior art keywords
- substrate
- temperature
- power supply
- heating
- cooling
- 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.)
- Abandoned
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Classifications
-
- 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
- C23C16/46—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 heating the substrate
- C23C16/463—Cooling of the substrate
-
- 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
- C23C16/46—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 heating the substrate
Abstract
ABSTRACT OF THE DISCLOSURE
An apparatus for forming, by a chemical vapor deposition process, a thin film of crystals such as diamond on a surface of a heated substrate placed in a reaction vessel. The apparatus has a substrate supporting structure, a heater for heating the substrate by heat conduction or by electric current supplied directly to the substrate, and a cooling device for cooling the substrate. The heater is controlled in accordance with the measured temperature of the substrate so as to accurately maintain the substrate temperature at a constant level.
An apparatus for forming, by a chemical vapor deposition process, a thin film of crystals such as diamond on a surface of a heated substrate placed in a reaction vessel. The apparatus has a substrate supporting structure, a heater for heating the substrate by heat conduction or by electric current supplied directly to the substrate, and a cooling device for cooling the substrate. The heater is controlled in accordance with the measured temperature of the substrate so as to accurately maintain the substrate temperature at a constant level.
Description
FIELD OF THE INVENTION
The present invention relates to an apparatus for forming a thin film by chemical vapor deposition (abbreviated as "CVD" hereinafter). More particularly, the 05 present invention is concerned with a chemical vapor forming apparatus suitable for forming a thin film of diamond, silicon, silicon dioxide, alumina, silicon carbide, silicon nitride, boron nitride and so forth.
DESCRIPl'ION OF THE RELATED ART
In recent years, thin films of diamond, silicon and so forth are finding increasing applications in various fields such as semiconductors, tools, machine parts, composite materials, nuclear plant components, and so on.
Conse~uently, the increase in applications has necessitated the need for higher ~uality films with dimensional stability. Many studies have been made for development of techniques for obtaining thin films of uniform quality and thickness.
For instance~ in case of vapor deposition of diamond, various methods have been proposedr for example, a hot filament CVD method disclosed in Japanese Examined Patent Publication No. 59-27753, a plasma CVD method of substrate heating type as disclosed in Japanese Unexamined Patent Publication No. 58-156594, a microwave plasma CVD method as disclosed in Japanese Examined Patent Publication No. 59--27754, and a cooling microwave plasma CVD method disclosed in Japanese Examined Patent Publication No. 62-21757.
The present invention relates to an apparatus for forming a thin film by chemical vapor deposition (abbreviated as "CVD" hereinafter). More particularly, the 05 present invention is concerned with a chemical vapor forming apparatus suitable for forming a thin film of diamond, silicon, silicon dioxide, alumina, silicon carbide, silicon nitride, boron nitride and so forth.
DESCRIPl'ION OF THE RELATED ART
In recent years, thin films of diamond, silicon and so forth are finding increasing applications in various fields such as semiconductors, tools, machine parts, composite materials, nuclear plant components, and so on.
Conse~uently, the increase in applications has necessitated the need for higher ~uality films with dimensional stability. Many studies have been made for development of techniques for obtaining thin films of uniform quality and thickness.
For instance~ in case of vapor deposition of diamond, various methods have been proposedr for example, a hot filament CVD method disclosed in Japanese Examined Patent Publication No. 59-27753, a plasma CVD method of substrate heating type as disclosed in Japanese Unexamined Patent Publication No. 58-156594, a microwave plasma CVD method as disclosed in Japanese Examined Patent Publication No. 59--27754, and a cooling microwave plasma CVD method disclosed in Japanese Examined Patent Publication No. 62-21757.
2~?~3~
Meanwhile, Kaneko et al. discloses the production of thin films by methods of hot filament typer substrate heating type and cooling typel at pp 546-552, Applied Surface Science Vol 33/34 (1988).
05 In the hot filament method disclosed in Japanese Examined Patent Publication No~ 59-27753, a filament is heated to about 2000C so as to decompose a source gas thereby producing active species which contribute to deposition of diamond. It is therefore necessary that a substrate is disposed within the reach of the active species. Usually, a hot filament is disposed at a position which is several millimeters from the substrate, so that the substrate receives a large quantity of heat radiated from the filament. It is therefore extremely difficult to maintain a given constant temperature of the substrate surface.
The microwave plasma CVD method disclosed in Japanese -~
Examined Patent Publication No. 59-27754 has difficulty in accurately controlling the substrate temperature, because the substrate temperature varies due to various factors including variations in the characteristics of plasma and variations ln the configuration and material of the substrate.
rrhe microwave plasma CVD method disclosed in Japanese Unexamined Patent Publication No. 58-156594 is intended to obviate the problems mentioned above, and employs means for heating the substrate thereby to control the substrate temperature. This method, relying upon positive heating of the substrate, can effectively be applied to the microwave plasma CVD method in which the substrate receives only a small quantity of heat from the substrate, but is not suitable in other methods in which the substrate receives a 05 large quantity of heat, such as the hot filament CVD method, plasma jet method and combustion flame method.
~ apanese Examined Patent Publication No. 62-21757 proposes a CVD method in which the substrate temperature is controlled by cooling the substrate using a coolant. This method, however, is unsatisfactory in that the substrate temperature is controllable only over a limited range and in that the temperature control cannot be conducted with a good response.
Thus, all these known CVD methods suffer from lS disadvanta~es in that the substrate temperature is controllable only in a limited temperature range and in that the temperature control cannot be effected with good response. It is understood that a t:echnique for controlling the substrate temperature is quite an important factor in the vapor deposition of diamond, for which no technique has been established for satisfactorily controlling the substrate temperature.
SUMMARY OF THE INVENTION
Accordingly, an object of the present invention is to provide a chemical vapor deposition apparatus for forming a thin film, capable of overcoming the above-described problems of the prior art.
One aspect of the present invent.ion provides an appara-tus for forming, by chemical ~apor deposition, a thin ~ilm on the surface of a heated substrate placed in a vessel, the apparatus comprising:
gas supplying and exhausting means for supplying a source gas into the vessel and exhausting the gas from the vessel;
decomposing means for decomposing the source gas;
substrate supporting means for supporting the substrate;
substrate cooling means for cooling the substrate;
substrate heating means for heating the substrate;
subskrate temperature measuring means for measuring the temperature of the substrate; and substrate temperature control means for controlling the temperature of said substrate.
In one preferred embodiment of the apparatus, the substrate heating means includes a heating electric power supply and power supply electrodes, and the substrate supporting means includes the power supply electrodes and the substrate cooling means, arranged such that the substrate is supported between :.. -. l , the power supply electrodes and the substrate coolin~ means, with an insulating means for insulating the. substrate cooling means from ~h~ substrate and the power supply electrodes, where-by the substrate is directly heated by the heat generated in the substrate by an electric current supplied through the power supply electrodes.
In another preferred embodiment of the apparatus, the ' - ~ : , , .
, . .
.:
substrate heating means includes a heating electric power supply and power supply electrodes, the power supply electrodes including -the substrate cooling means. -In yet another preferred embodiment of the apparatus, the substrate temperature measuring means measures, in a non-contacting manner, the temperature of the surface of the substrate which is opposite to the substrate surface on which the film is formed.
In a still preferred embodiment of the apparatus, the thin film is made of diamond.
Arlother aspect of the present invention provides a process for forming a thin film, comprising the steps of:
providing a substrate in a vessel;
heating the substrate;
supplying a source gas to the vessel, decomposing the source gas, and exhausting the resultant gas ~rom the ~essel;
depositing a thin film on the substrate by chemical ~ .
vapor deposition while simultaneously heating and cooling the substrate, measuring a temperature of the substrate and varying the heating in response to the temperature.
In one preferred embodiment of the process the heating is conducted by electric power and the cooling is conducted by water.
In another preferred embodiment of the process, during the deposition, the temperature is maintained substantially - 5a -A
73~61-16 constant.
BRIEF DESCRIPTION OF THE DRA~INGS
Figure 1 is a sehematic illustration of an embodiment of a chemical vapor deposition apparatus of the invention for ~orming a thin filmî
:: Figure 2 is a sehematic perspective view of a substrate supporting device with a temperature eontroller, used in another embodiment of the present invention;
~ Figure 3 is a schematle illustration of an electrie : 10: power supply holder with a temperature controller, used in still another embodiment of the present lnvention) `'"
..
,~, ,,:
'' - 5b -: . . . . . . .
~.
~ ~3 ~ ~a ~
Fig. 4 is a schematic perspective view of another example of the power supply holder of the present invention;
and Fig. 5 is a diagram showing the relationship between 05 the substrate temperature and the growth rate and the quality of the diamond thin film.
DESCRIPTION OF T~E PREFERR~D EMBODIMENTS
The invention will be described in more detail with reference to the drawings.
Fig. 1 is a schematic illustration of an embodiment of the apparatus of the present invention, applied to a system for forming a thin film by chemical vapor deposition employing a hot filament.
The present inventors have discovered the following facts in the course of a further study. Namelyr the inventors have found that a relationship as shown in Fig.5 exists between the substrate temperature and the rate of growth of diamond, as well as the quality of the crystal.
In Fig. 5, the quality of the crystal is expressed in terms of a ratio Ind/Id between the pea~ intensity Ind of non-diamond carbon as impurity and the peak intensity Id of diamond, the peak intensities being determined through Raman spectral analysis of the deposited diamond. Thus, a smaller value o~ the ratio Ind/In indicates better quality of the diamond crystal.
From Fig. 5~ it is understood that the growth rate and the purity of the diamond can be freely controlled by suitably setting the substrate temperature. For instance, a $ ~
diamond of a high purity can be deposited at a low substrate temperature TA, whereas deposition at a substrate temperature TB enables diamond to deposit at a high growth rate although the purity is slightly reduced. Thus, in the 05 CVD process for depositing diamond, it is necessary that the substrate temperature is controlled over a wide range and with good accuracy, in order to obtain a desired quality and growth rate of crystalO
For instance~ when the substrate temperature which has been maintained at TA during deposition is shifted to a higher temperature for any reason~ the purity of the diamond is seriously decreased. Conversely, when the substrate temperature is shifted to a lower temperature from TB during the deposition, the crystal growth rate is lowered to make it impossible to obtain the required amount of deposition within a given time. Thus, minimization of fluctuation of the substrate temperature during deposition also is a very important factor The apparatus has a reaction vessel 1 provided with a pressure gauge 17. The reaction vessel 1 accommodates a substrate supporting de~ice 3 for supporting a substrate 2 on which a thin film is to be formed by deposition. The reaction vessel 1 also is provided with a work port 11 through which the substrate 2 is brought into and out of the reaction vessel 1. The substrate supporting device 3 includes heating means 4 for heating the substrate 2 and a cooling means 5 under the heating means 4.
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The heating means 4 includes a thermocouple 13 and is capable of heating the substrate 2 when supplied with electric power through power terminals 12, while the cooling means 5 includes a cooling pipe 14 for circulating cooling 05 water~ a flowmeter 15 and a thermometer 16 for cooling water.
The reaction vessel 1 also is provided at its upper or lower portions with a source gas supply port 7 and a gas exhaust port 8. A source gas such as CH4 gas diluted with H2 gas is introduced into the reaction vessel 1 through the source gas supply port 7 and is subjected to decompose and the resultant gas is exhausted through the exhaust port 8 by means of a vacuum pump 19. In order to thermally decompose the source gas, a hot filament 6 is disposed in the reaction vessel 1 which filament is connected to a power supply 18.
In this case, a plasma may be used in place of the filament, as the decomposing means for decomposin~ the source gas.
It is possible to provide a non-contact type thermometer 9, e.g., a radiation pyrometer~ outside the reaction vessel 1 to enable measurement of the substrate temperature through a window 20 attached to the wall of the reaction vessel 1.
The apparatus has temperature control means 10 which includes, for example, a thermocouple voltage converter 21, a PID controller 22 and a thyristor regulator 23 for controlling the electric power supplied to the substrate heating means 4. The temperature controller 10 controls the 2~
operation of the heating means ~ in accordance with the substrate temperature measured by the non-contact type thermometer 9 or the thermocouple 13, thereb~ controlling the substrate temperature in combination with the cooling 05 means 5. A switch 24 is provided for enabling change-over between the thermocouple 13 and the non-contact thermometer 9.
The described arrangement in the apparatus of the present invention enables a control of the substrate temperature over a much wider temperature range than in known apparatuses in which the substrate temperature is controlled solely by heating or cooling. In normal operation of this apparatus, both the electric power and the cooling water are simultaneously supplied and the level of the electrical current is varied in accordance with a change in the substrate temperature, thereby maintaining the substrate temperature at a constant level. According to this method, the substrate temperature can be controlled with much higher response speed and much better accuracy than in the case where the substrate temperature is controlled through a control of flow rate of the cooling water. In additionr there is no risk of boiling of the cooling water because a certain sufficient flow rate of the cooling water is maintained.
Another embodiment of the present invention, having a substrate supporting device 3, heating means 4 and cooling means 5 different from those in the first embodiment, will ~ ~ ~ 3 ~ ", !~
be described with reference to Fig. 2 which is a schematic perspective view of this embodiment.
In this embodiment, the substrate supporting device 3 for supporting a substrate 2 is a metal bar 31 on an upper 05 portion of which is provided an RF heating coil 32 as the heating means 4, while a cooling water pipe 14 as the cooling means 5 is provided on a lower portion of the metal bar 31 by silver brazing.
As a result of a study described below, the present inventors also have considered an arrangement in which a substrate is held by a power supply holder which also serves as electrodes, the holder holding the substrate being placed in a reaction vessel of a reduced pressure so that an electric current is supplied throuyh the power supply holder so as to heat the substrate.
Namely, the inventors prepared test pieces of silicon substrates 50 mm long and 10 mm wide. The inventors connected electrodes to both ends of the test piece and supplied electric current to the test piece through these electrodes. The test piece was not red-heated at all when the voltage applied is still low. However, when the voltage applied was raised to 100 V, the substrate test piece was suddenly red-heated while drastically reducing its resistance from several kQ to several Q or below. It was confirmed through a measurement by a radiation pyrometer that the substrate surface temperature can be raised up to 1300C by this methodO In addition, the substrate test piece was uniformly red-heated over the entire portion ~3~ 'J~q~
thereof and enabled accurate measurement of the surface temperature. It was also confirmed that the temperature control can be done in a stable manner because the power supply holder, which will be detailed later, can stably hold oS the substrate without substantial change in the resistances at the contacts between the holder and the substrate.
This apparatus will be described in detail with reference to Fig. 3.
Referring to Fig. 3,the apparatus employs a hot filament 6 for thermally decomposing the source gas. The apparatus also has a heating electric power supply 43 for supplying electric power which heats the substrate 2. A
power supply holder 41 includes a power supply electrode 42 and an insulating means 44 for insulating the cooling means 5 from the substrate 2 and the power supply electrodes. The power supply holder 41 is capable of ho~ding the substrate 2 and supplying the substrate 2 with an electric current from the heating electric power supply 43. The apparatus also has cooling means 5 which is held in contact with the power supply electrodes 42 through the insulating means 44.
Numeral 47 designates a nozzle made of quartz which corresponds to the source gas supply port 7 and is capable of introducing the source ~as into the zone near the surface of the substrate ~. Numeral 9 denotes a radiation pyrometer capable o~ measuring the substrate temperature in a non-contact manner. These components, except the radiation pyrometer, are encased in a reaction vessel as in the case of the embodiment shown in Fig. 1. The substrate 2 is disposed in the reaction vessel 1 such that its major surfaces are held vertically. This, however, is not exclusive and the power supply holder 41 and other components may be arranged horizontally so that the major 05 surfaces of the substrate 2 extend substantially horizontally as in Fig. 1.
The aforementioned radiation pyrometer g is disposed to oppose the reverse side, i.e.,the side opposite to the thin film depositing surface, of the substrate 2. The substrate 2, due to its high heat conductivity, exhibits almost the same temperature at both of its surfaces. It is therefore possible to accurately measure the temperature of the thin film depositing surface of the substrate by the radiation pyrometer 9 which senses the temperature of the sur~ace of the substrate opposite to the depositing surface. If the substrate temperature is measured directly by contacting a thermocouple to the thin film depositing surface, a measuring error may be caused by influence of the heat radiated from the ~ilament 6. Such an error, however, can be eliminated and a high accuracy of the temperature measurement is attained since the temperature is sensed and measured by the radiation pyrometer 9 which faces the reverse side of the substrate 2.
In order to ensure an electrical insulation, the insulating means 44 are interposed between the cooling means 5 such as copper chill blocks and the power supply electrodes 42. More specifically, the arrangement is such that substrate 2 is received in slits 46 formed in the power 2~3~
supply electrodes 42 and pressing screws 45 are tightened to fix the substrate 2 between the power supply electrodes 42 and the insulating means 44. The insulating means 44 may be formed of an insulating material such as aluminum nitride 05 plate. Although a quartz plate 2 can be used as the material of the insulating means 44, the use of aluminum nitride is preferred because this material exhibits a greater insulation and higher thermal conductivity than quartz. If the cooling means 5 is made of an insulating ; 10 material or if the surface of the cooling means 5 is insulated, it is not necessary to interpose insulating means between the cooling means 5 and the electrodes 42.
In view of large electrical currents supplied through the power supply electrodes 42, each power supply electrode 42 has a large cross-sectional area so as to reduce electrical resistance therethrough and is constructed to tightly contact with a large surfac~e area of the substrate 2 so as to reduce the electrical and heat resistance across the ontact between the power supply electrode 42 and the substrate 2.
Fig.4 is a perspective view of another example of the power supply holder.
The power supply holder employs a cooling means 5 through which cooling water is circulated. The substrate 2 is placed on the cooling means 5 such that the whole area of one surface of the substrate 2 contacts the cooling means 5.
A pair of electrodes 42 are positioned in contact with two spaced portions of the upper surface of the substrate 2 so ' 2 ~ , that the substrate 2 can be supplied with electric power through these electrodes 42 from a heating electric power supply ~3~ Thus, the substrate 2 itself functions as the heating means by electrically heating with electric power 05 supplied thereto. When the cooling means 5 is made of an electrically conductive material such as copper, it is necessary that an insulating means ~4 is placed between the substrate 2 and the cooling means 5 as illustrated.
Example l Diamond was deposited by hot filament CYD method, using the apparatus of the invention shown in Fig. l. In order to attain a large density of diamond nucleation, a silicon plate of lO mm wide, 20 mm long and 0.5 mm thickf was ground by diamond grains of particle size of about 20 ~um, and used as the substrate 2. A tungsten filament 6 was set at a position about 2 mm apart from the deposition surface. At the same time, a source gas supply nozzle for supplying a source gas, which is a mixture of methane and hydrogen, was set such that the end of the nozzle is about 5 mm spaced apart from the deposition surface. The temperature of the filament during deposition was measured by an optical pyrometer,while the substrate temperature was measured by a sheet-type thermocouple of 0.07 mm thick.
During the deposition, the power supply to the substrate 2 was adjusted so as to maintain the substrate temperature at any desired temperature between 500 and 1200C. The temperature control could be done with a very small error of less than ~ 0.5OC. The deposition was 2 ~
conducted under the conditions of: a methane flow rate of 5 sccm, hydrogen flow rate of 50~ sccm, atmospheric pressure of 30 Torr, filament temperature of 2100C and substrate temperature of 850C.
05 Deposition of diamond ~ilm was confirmed by an observation throuyh a scanning electron microscope and by Raman spectral analysis. A section of the film was observed by the scanning electron microscope for the measurement of the film thickness. The film growth rate was calculated from the film thickness to be 10 ~m/hr. ~ micro-Raman spectral analysis was conducted on a plurality of points on a section of the film o~ 23 ~m thick, for the measurement of the peak intensity Id exhibited by diamond and peak intensity Ind exhibited by non-diamond carbon. All these measuring points exhibited the same value of the ratio Ind/Id. The cooling was conducted by circulating cooling water of 25C at a flow rate of 3 ~/min.
Example 2 A description will be given of the result of a test in which diamond was formed on the substrate by CVD p~ocess employing a co~bination of the apparatus shown in Fig. 1 and the power supply holder of the type shown in Fig. 3. The CVD proces was carried out by using, as the source gasl CH4 gas diluted with hydrogen gas to 1~ concentration. The source gas was supplied from the nozzle at a rate of 2~0 sccm onto the substrate 2 placed in the reaction vessel 1 in which an atmosphere of 30 Torr or lower pressure was maintained. The command substrate temperature was 870C. A
2 ~ 'f~1 ~
silicon plate of lO mm wide, 20 mm long and 0.5 mm thick was used as the substrate. In this example, the temperature of the substrate surface could be controlled with a very small error of ~ 0. 20C with respect to the command temperature of 05 870OC, by virtue of the heating of the substrate with electrical current supplied to the substrate itself.
The diamond film formed by this process exhibited a resistivity of 1013 to 1014 Qm and a hardness Hv of 8000 to 90G0 which well approximate those of natural diamonds, over the entire area of the film.
From the foregoing description, it will be understood that the apparatus of the present invention makes it possible to form a thin film of uniform thickness and quality.
Although the invention has been described through its specific forms, it is to be understood that the described embodiments are not exclusive. For instance, although hot filament CVD method is used in the first and second embodiments, the apparatus of the present invention can equally be applied to other CVD processes such as plasma-assisted CVD and to PVD (physical vapor deposition) processes such as sputtering P~D, and thin films of superior quaIity can be obtained also in such applications.
Meanwhile, Kaneko et al. discloses the production of thin films by methods of hot filament typer substrate heating type and cooling typel at pp 546-552, Applied Surface Science Vol 33/34 (1988).
05 In the hot filament method disclosed in Japanese Examined Patent Publication No~ 59-27753, a filament is heated to about 2000C so as to decompose a source gas thereby producing active species which contribute to deposition of diamond. It is therefore necessary that a substrate is disposed within the reach of the active species. Usually, a hot filament is disposed at a position which is several millimeters from the substrate, so that the substrate receives a large quantity of heat radiated from the filament. It is therefore extremely difficult to maintain a given constant temperature of the substrate surface.
The microwave plasma CVD method disclosed in Japanese -~
Examined Patent Publication No. 59-27754 has difficulty in accurately controlling the substrate temperature, because the substrate temperature varies due to various factors including variations in the characteristics of plasma and variations ln the configuration and material of the substrate.
rrhe microwave plasma CVD method disclosed in Japanese Unexamined Patent Publication No. 58-156594 is intended to obviate the problems mentioned above, and employs means for heating the substrate thereby to control the substrate temperature. This method, relying upon positive heating of the substrate, can effectively be applied to the microwave plasma CVD method in which the substrate receives only a small quantity of heat from the substrate, but is not suitable in other methods in which the substrate receives a 05 large quantity of heat, such as the hot filament CVD method, plasma jet method and combustion flame method.
~ apanese Examined Patent Publication No. 62-21757 proposes a CVD method in which the substrate temperature is controlled by cooling the substrate using a coolant. This method, however, is unsatisfactory in that the substrate temperature is controllable only over a limited range and in that the temperature control cannot be conducted with a good response.
Thus, all these known CVD methods suffer from lS disadvanta~es in that the substrate temperature is controllable only in a limited temperature range and in that the temperature control cannot be effected with good response. It is understood that a t:echnique for controlling the substrate temperature is quite an important factor in the vapor deposition of diamond, for which no technique has been established for satisfactorily controlling the substrate temperature.
SUMMARY OF THE INVENTION
Accordingly, an object of the present invention is to provide a chemical vapor deposition apparatus for forming a thin film, capable of overcoming the above-described problems of the prior art.
One aspect of the present invent.ion provides an appara-tus for forming, by chemical ~apor deposition, a thin ~ilm on the surface of a heated substrate placed in a vessel, the apparatus comprising:
gas supplying and exhausting means for supplying a source gas into the vessel and exhausting the gas from the vessel;
decomposing means for decomposing the source gas;
substrate supporting means for supporting the substrate;
substrate cooling means for cooling the substrate;
substrate heating means for heating the substrate;
subskrate temperature measuring means for measuring the temperature of the substrate; and substrate temperature control means for controlling the temperature of said substrate.
In one preferred embodiment of the apparatus, the substrate heating means includes a heating electric power supply and power supply electrodes, and the substrate supporting means includes the power supply electrodes and the substrate cooling means, arranged such that the substrate is supported between :.. -. l , the power supply electrodes and the substrate coolin~ means, with an insulating means for insulating the. substrate cooling means from ~h~ substrate and the power supply electrodes, where-by the substrate is directly heated by the heat generated in the substrate by an electric current supplied through the power supply electrodes.
In another preferred embodiment of the apparatus, the ' - ~ : , , .
, . .
.:
substrate heating means includes a heating electric power supply and power supply electrodes, the power supply electrodes including -the substrate cooling means. -In yet another preferred embodiment of the apparatus, the substrate temperature measuring means measures, in a non-contacting manner, the temperature of the surface of the substrate which is opposite to the substrate surface on which the film is formed.
In a still preferred embodiment of the apparatus, the thin film is made of diamond.
Arlother aspect of the present invention provides a process for forming a thin film, comprising the steps of:
providing a substrate in a vessel;
heating the substrate;
supplying a source gas to the vessel, decomposing the source gas, and exhausting the resultant gas ~rom the ~essel;
depositing a thin film on the substrate by chemical ~ .
vapor deposition while simultaneously heating and cooling the substrate, measuring a temperature of the substrate and varying the heating in response to the temperature.
In one preferred embodiment of the process the heating is conducted by electric power and the cooling is conducted by water.
In another preferred embodiment of the process, during the deposition, the temperature is maintained substantially - 5a -A
73~61-16 constant.
BRIEF DESCRIPTION OF THE DRA~INGS
Figure 1 is a sehematic illustration of an embodiment of a chemical vapor deposition apparatus of the invention for ~orming a thin filmî
:: Figure 2 is a sehematic perspective view of a substrate supporting device with a temperature eontroller, used in another embodiment of the present invention;
~ Figure 3 is a schematle illustration of an electrie : 10: power supply holder with a temperature controller, used in still another embodiment of the present lnvention) `'"
..
,~, ,,:
'' - 5b -: . . . . . . .
~.
~ ~3 ~ ~a ~
Fig. 4 is a schematic perspective view of another example of the power supply holder of the present invention;
and Fig. 5 is a diagram showing the relationship between 05 the substrate temperature and the growth rate and the quality of the diamond thin film.
DESCRIPTION OF T~E PREFERR~D EMBODIMENTS
The invention will be described in more detail with reference to the drawings.
Fig. 1 is a schematic illustration of an embodiment of the apparatus of the present invention, applied to a system for forming a thin film by chemical vapor deposition employing a hot filament.
The present inventors have discovered the following facts in the course of a further study. Namelyr the inventors have found that a relationship as shown in Fig.5 exists between the substrate temperature and the rate of growth of diamond, as well as the quality of the crystal.
In Fig. 5, the quality of the crystal is expressed in terms of a ratio Ind/Id between the pea~ intensity Ind of non-diamond carbon as impurity and the peak intensity Id of diamond, the peak intensities being determined through Raman spectral analysis of the deposited diamond. Thus, a smaller value o~ the ratio Ind/In indicates better quality of the diamond crystal.
From Fig. 5~ it is understood that the growth rate and the purity of the diamond can be freely controlled by suitably setting the substrate temperature. For instance, a $ ~
diamond of a high purity can be deposited at a low substrate temperature TA, whereas deposition at a substrate temperature TB enables diamond to deposit at a high growth rate although the purity is slightly reduced. Thus, in the 05 CVD process for depositing diamond, it is necessary that the substrate temperature is controlled over a wide range and with good accuracy, in order to obtain a desired quality and growth rate of crystalO
For instance~ when the substrate temperature which has been maintained at TA during deposition is shifted to a higher temperature for any reason~ the purity of the diamond is seriously decreased. Conversely, when the substrate temperature is shifted to a lower temperature from TB during the deposition, the crystal growth rate is lowered to make it impossible to obtain the required amount of deposition within a given time. Thus, minimization of fluctuation of the substrate temperature during deposition also is a very important factor The apparatus has a reaction vessel 1 provided with a pressure gauge 17. The reaction vessel 1 accommodates a substrate supporting de~ice 3 for supporting a substrate 2 on which a thin film is to be formed by deposition. The reaction vessel 1 also is provided with a work port 11 through which the substrate 2 is brought into and out of the reaction vessel 1. The substrate supporting device 3 includes heating means 4 for heating the substrate 2 and a cooling means 5 under the heating means 4.
2~$~
The heating means 4 includes a thermocouple 13 and is capable of heating the substrate 2 when supplied with electric power through power terminals 12, while the cooling means 5 includes a cooling pipe 14 for circulating cooling 05 water~ a flowmeter 15 and a thermometer 16 for cooling water.
The reaction vessel 1 also is provided at its upper or lower portions with a source gas supply port 7 and a gas exhaust port 8. A source gas such as CH4 gas diluted with H2 gas is introduced into the reaction vessel 1 through the source gas supply port 7 and is subjected to decompose and the resultant gas is exhausted through the exhaust port 8 by means of a vacuum pump 19. In order to thermally decompose the source gas, a hot filament 6 is disposed in the reaction vessel 1 which filament is connected to a power supply 18.
In this case, a plasma may be used in place of the filament, as the decomposing means for decomposin~ the source gas.
It is possible to provide a non-contact type thermometer 9, e.g., a radiation pyrometer~ outside the reaction vessel 1 to enable measurement of the substrate temperature through a window 20 attached to the wall of the reaction vessel 1.
The apparatus has temperature control means 10 which includes, for example, a thermocouple voltage converter 21, a PID controller 22 and a thyristor regulator 23 for controlling the electric power supplied to the substrate heating means 4. The temperature controller 10 controls the 2~
operation of the heating means ~ in accordance with the substrate temperature measured by the non-contact type thermometer 9 or the thermocouple 13, thereb~ controlling the substrate temperature in combination with the cooling 05 means 5. A switch 24 is provided for enabling change-over between the thermocouple 13 and the non-contact thermometer 9.
The described arrangement in the apparatus of the present invention enables a control of the substrate temperature over a much wider temperature range than in known apparatuses in which the substrate temperature is controlled solely by heating or cooling. In normal operation of this apparatus, both the electric power and the cooling water are simultaneously supplied and the level of the electrical current is varied in accordance with a change in the substrate temperature, thereby maintaining the substrate temperature at a constant level. According to this method, the substrate temperature can be controlled with much higher response speed and much better accuracy than in the case where the substrate temperature is controlled through a control of flow rate of the cooling water. In additionr there is no risk of boiling of the cooling water because a certain sufficient flow rate of the cooling water is maintained.
Another embodiment of the present invention, having a substrate supporting device 3, heating means 4 and cooling means 5 different from those in the first embodiment, will ~ ~ ~ 3 ~ ", !~
be described with reference to Fig. 2 which is a schematic perspective view of this embodiment.
In this embodiment, the substrate supporting device 3 for supporting a substrate 2 is a metal bar 31 on an upper 05 portion of which is provided an RF heating coil 32 as the heating means 4, while a cooling water pipe 14 as the cooling means 5 is provided on a lower portion of the metal bar 31 by silver brazing.
As a result of a study described below, the present inventors also have considered an arrangement in which a substrate is held by a power supply holder which also serves as electrodes, the holder holding the substrate being placed in a reaction vessel of a reduced pressure so that an electric current is supplied throuyh the power supply holder so as to heat the substrate.
Namely, the inventors prepared test pieces of silicon substrates 50 mm long and 10 mm wide. The inventors connected electrodes to both ends of the test piece and supplied electric current to the test piece through these electrodes. The test piece was not red-heated at all when the voltage applied is still low. However, when the voltage applied was raised to 100 V, the substrate test piece was suddenly red-heated while drastically reducing its resistance from several kQ to several Q or below. It was confirmed through a measurement by a radiation pyrometer that the substrate surface temperature can be raised up to 1300C by this methodO In addition, the substrate test piece was uniformly red-heated over the entire portion ~3~ 'J~q~
thereof and enabled accurate measurement of the surface temperature. It was also confirmed that the temperature control can be done in a stable manner because the power supply holder, which will be detailed later, can stably hold oS the substrate without substantial change in the resistances at the contacts between the holder and the substrate.
This apparatus will be described in detail with reference to Fig. 3.
Referring to Fig. 3,the apparatus employs a hot filament 6 for thermally decomposing the source gas. The apparatus also has a heating electric power supply 43 for supplying electric power which heats the substrate 2. A
power supply holder 41 includes a power supply electrode 42 and an insulating means 44 for insulating the cooling means 5 from the substrate 2 and the power supply electrodes. The power supply holder 41 is capable of ho~ding the substrate 2 and supplying the substrate 2 with an electric current from the heating electric power supply 43. The apparatus also has cooling means 5 which is held in contact with the power supply electrodes 42 through the insulating means 44.
Numeral 47 designates a nozzle made of quartz which corresponds to the source gas supply port 7 and is capable of introducing the source ~as into the zone near the surface of the substrate ~. Numeral 9 denotes a radiation pyrometer capable o~ measuring the substrate temperature in a non-contact manner. These components, except the radiation pyrometer, are encased in a reaction vessel as in the case of the embodiment shown in Fig. 1. The substrate 2 is disposed in the reaction vessel 1 such that its major surfaces are held vertically. This, however, is not exclusive and the power supply holder 41 and other components may be arranged horizontally so that the major 05 surfaces of the substrate 2 extend substantially horizontally as in Fig. 1.
The aforementioned radiation pyrometer g is disposed to oppose the reverse side, i.e.,the side opposite to the thin film depositing surface, of the substrate 2. The substrate 2, due to its high heat conductivity, exhibits almost the same temperature at both of its surfaces. It is therefore possible to accurately measure the temperature of the thin film depositing surface of the substrate by the radiation pyrometer 9 which senses the temperature of the sur~ace of the substrate opposite to the depositing surface. If the substrate temperature is measured directly by contacting a thermocouple to the thin film depositing surface, a measuring error may be caused by influence of the heat radiated from the ~ilament 6. Such an error, however, can be eliminated and a high accuracy of the temperature measurement is attained since the temperature is sensed and measured by the radiation pyrometer 9 which faces the reverse side of the substrate 2.
In order to ensure an electrical insulation, the insulating means 44 are interposed between the cooling means 5 such as copper chill blocks and the power supply electrodes 42. More specifically, the arrangement is such that substrate 2 is received in slits 46 formed in the power 2~3~
supply electrodes 42 and pressing screws 45 are tightened to fix the substrate 2 between the power supply electrodes 42 and the insulating means 44. The insulating means 44 may be formed of an insulating material such as aluminum nitride 05 plate. Although a quartz plate 2 can be used as the material of the insulating means 44, the use of aluminum nitride is preferred because this material exhibits a greater insulation and higher thermal conductivity than quartz. If the cooling means 5 is made of an insulating ; 10 material or if the surface of the cooling means 5 is insulated, it is not necessary to interpose insulating means between the cooling means 5 and the electrodes 42.
In view of large electrical currents supplied through the power supply electrodes 42, each power supply electrode 42 has a large cross-sectional area so as to reduce electrical resistance therethrough and is constructed to tightly contact with a large surfac~e area of the substrate 2 so as to reduce the electrical and heat resistance across the ontact between the power supply electrode 42 and the substrate 2.
Fig.4 is a perspective view of another example of the power supply holder.
The power supply holder employs a cooling means 5 through which cooling water is circulated. The substrate 2 is placed on the cooling means 5 such that the whole area of one surface of the substrate 2 contacts the cooling means 5.
A pair of electrodes 42 are positioned in contact with two spaced portions of the upper surface of the substrate 2 so ' 2 ~ , that the substrate 2 can be supplied with electric power through these electrodes 42 from a heating electric power supply ~3~ Thus, the substrate 2 itself functions as the heating means by electrically heating with electric power 05 supplied thereto. When the cooling means 5 is made of an electrically conductive material such as copper, it is necessary that an insulating means ~4 is placed between the substrate 2 and the cooling means 5 as illustrated.
Example l Diamond was deposited by hot filament CYD method, using the apparatus of the invention shown in Fig. l. In order to attain a large density of diamond nucleation, a silicon plate of lO mm wide, 20 mm long and 0.5 mm thickf was ground by diamond grains of particle size of about 20 ~um, and used as the substrate 2. A tungsten filament 6 was set at a position about 2 mm apart from the deposition surface. At the same time, a source gas supply nozzle for supplying a source gas, which is a mixture of methane and hydrogen, was set such that the end of the nozzle is about 5 mm spaced apart from the deposition surface. The temperature of the filament during deposition was measured by an optical pyrometer,while the substrate temperature was measured by a sheet-type thermocouple of 0.07 mm thick.
During the deposition, the power supply to the substrate 2 was adjusted so as to maintain the substrate temperature at any desired temperature between 500 and 1200C. The temperature control could be done with a very small error of less than ~ 0.5OC. The deposition was 2 ~
conducted under the conditions of: a methane flow rate of 5 sccm, hydrogen flow rate of 50~ sccm, atmospheric pressure of 30 Torr, filament temperature of 2100C and substrate temperature of 850C.
05 Deposition of diamond ~ilm was confirmed by an observation throuyh a scanning electron microscope and by Raman spectral analysis. A section of the film was observed by the scanning electron microscope for the measurement of the film thickness. The film growth rate was calculated from the film thickness to be 10 ~m/hr. ~ micro-Raman spectral analysis was conducted on a plurality of points on a section of the film o~ 23 ~m thick, for the measurement of the peak intensity Id exhibited by diamond and peak intensity Ind exhibited by non-diamond carbon. All these measuring points exhibited the same value of the ratio Ind/Id. The cooling was conducted by circulating cooling water of 25C at a flow rate of 3 ~/min.
Example 2 A description will be given of the result of a test in which diamond was formed on the substrate by CVD p~ocess employing a co~bination of the apparatus shown in Fig. 1 and the power supply holder of the type shown in Fig. 3. The CVD proces was carried out by using, as the source gasl CH4 gas diluted with hydrogen gas to 1~ concentration. The source gas was supplied from the nozzle at a rate of 2~0 sccm onto the substrate 2 placed in the reaction vessel 1 in which an atmosphere of 30 Torr or lower pressure was maintained. The command substrate temperature was 870C. A
2 ~ 'f~1 ~
silicon plate of lO mm wide, 20 mm long and 0.5 mm thick was used as the substrate. In this example, the temperature of the substrate surface could be controlled with a very small error of ~ 0. 20C with respect to the command temperature of 05 870OC, by virtue of the heating of the substrate with electrical current supplied to the substrate itself.
The diamond film formed by this process exhibited a resistivity of 1013 to 1014 Qm and a hardness Hv of 8000 to 90G0 which well approximate those of natural diamonds, over the entire area of the film.
From the foregoing description, it will be understood that the apparatus of the present invention makes it possible to form a thin film of uniform thickness and quality.
Although the invention has been described through its specific forms, it is to be understood that the described embodiments are not exclusive. For instance, although hot filament CVD method is used in the first and second embodiments, the apparatus of the present invention can equally be applied to other CVD processes such as plasma-assisted CVD and to PVD (physical vapor deposition) processes such as sputtering P~D, and thin films of superior quaIity can be obtained also in such applications.
Claims (19)
1. An apparatus for forming, by chemical vapor deposition, a thin film on a surface of a heated substrate placed in a vessel, said apparatus comprising:
gas supplying and exhausting means for supplying a source gas into said vessel and exhausting the resultant gas from said vessel;
decomposing means for decomposing said source gas;
substrate supporting means for supporting said substrate;
substrate cooling means for cooling said substrate;
substrate heating means for heating said substrate;
substrate temperature measuring means for measuring a temperature of said substrate; and substrate temperature control means for controlling said temperature of said substrate.
gas supplying and exhausting means for supplying a source gas into said vessel and exhausting the resultant gas from said vessel;
decomposing means for decomposing said source gas;
substrate supporting means for supporting said substrate;
substrate cooling means for cooling said substrate;
substrate heating means for heating said substrate;
substrate temperature measuring means for measuring a temperature of said substrate; and substrate temperature control means for controlling said temperature of said substrate.
2. An apparatus according to Claim 1, wherein said substrate heating means includes a heating electric power supply and power supply electrodes, and said substrate supporting means includes said power supply electrodes and said substrate cooling means, arranged such that said substrate is supported between said power supply electrodes and said substrate cooling means, with an insulating means for insulating said substrate cooling means from said substrate and said power supply electrodes, whereby said substrate is directly heated by the heat generated in said substrate by an electric current supplied through said power supply electrodes.
3. An apparatus according to Claim 1, wherein said substrate heating means includes a heating electric power supply and power supply electrodes, said power supply electrodes including said substrate cooling means.
4. An apparatus according to Claim 1, wherein said substrate temperature measuring means measures, in a non-contacting manner, the temperature of the surface of said substrate which is opposite to the substrate surface on which said film is formed.
5. An apparatus according to Claim 1, wherein said thin film is a film of diamond.
6. A process for forming a thin film, comprising the steps of:
providing a substrate in a vessel;
heating said substrate;
supplying a source gas to said vessel, decomposing said source gas, and exhausting the resultant gas from said vessel;
depositing a thin film on said substrate by chemical vapor deposition while simultaneously heating and cooling said substrate, measuring a temperature of said substrate and varying said heating in response to said temperature.
providing a substrate in a vessel;
heating said substrate;
supplying a source gas to said vessel, decomposing said source gas, and exhausting the resultant gas from said vessel;
depositing a thin film on said substrate by chemical vapor deposition while simultaneously heating and cooling said substrate, measuring a temperature of said substrate and varying said heating in response to said temperature.
7. The process according to claim 6 wherein said heating is conducted by electric power and said cooling is conducted by water.
8. The process of claim 6, wherein during the deposition, the temperature of the substrate is maintained substantially constant.
9. The process of claim 6, 7 or 8, wherein the thin film is of diamond.
10. The process of claim 9, wherein CH4 gas diluted with H2 gas is employed as the source gas.
11. The process of claim 10, wherein the substrate is made of silicon.
12. The process of claim 9, wherein the temperature of the substrate is maintained within + 0.5°C of a predetermined temperature at which diamond is formed.
13. The process of claim 12, wherein the predetermined temperature is from about 850 to about 870°C.
14. The process of claim 6, 7 or 8, which is conducted by using an apparatus comprising:
gas supplying and exhausting means for supplying a source gas into the vessel and exhausting the resultant gas from the vessel;
decomposing means for decomposing the source gas;
substrate supporting means for supporing the substrate;
substrate cooling means for cooling the substrate;
substrate heating means for heating the substrate;
substrate temperature measuring means for measuring a temperature of the substrate; and substrate temperature control means for controlling the temperature of the substrate.
gas supplying and exhausting means for supplying a source gas into the vessel and exhausting the resultant gas from the vessel;
decomposing means for decomposing the source gas;
substrate supporting means for supporing the substrate;
substrate cooling means for cooling the substrate;
substrate heating means for heating the substrate;
substrate temperature measuring means for measuring a temperature of the substrate; and substrate temperature control means for controlling the temperature of the substrate.
15. The process of claim 14, wherein in the apparatus, the substrate heating means includes a heating electro power supply and power supply electrodes, and the substrate supporting means includes the power supply electrodes and the substrate cooling means, arranged such that the substrate is supported between the power supply electrodes and the substrate cooling means, with an insulating means for insulating the substrate cooling means from the substrate and the power supply electrodes, whereby the sub-strate is directly heated by the heat generated in the substrate by an electric current supplied through the power supply elec-trodes.
16. The process of claim 15, wherein the thin film is of diamond.
17. The process of claim 16, wherein CH4 gas diluted with H2 gas is employed as the source gas.
18. The process of claim 17, wherein the substrate is made of silicon.
19. An apparatus according to any one of claims 1 to 5, wherein the substrate is made of silicon.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31250989 | 1989-12-01 | ||
| JP312509/1989 | 1989-12-01 | ||
| JP3949590A JPH02289494A (en) | 1989-02-22 | 1990-02-20 | Synthesizing device for diamond |
| JP39495/1990 | 1990-02-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2023684A1 true CA2023684A1 (en) | 1991-06-02 |
Family
ID=26378907
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002023684A Abandoned CA2023684A1 (en) | 1989-12-01 | 1990-08-21 | Chemical vapor deposition apparatus for forming thin film |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US5225245A (en) |
| EP (1) | EP0436070B1 (en) |
| CA (1) | CA2023684A1 (en) |
| DE (1) | DE69016633T2 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09157846A (en) * | 1995-12-01 | 1997-06-17 | Teisan Kk | Temperature controller |
| KR100551980B1 (en) | 1997-11-03 | 2006-02-20 | 에이에스엠 아메리카, 인코포레이티드 | Method and Apparatus of Processing Wafers with Low Mass Support |
| JP4294140B2 (en) * | 1999-01-27 | 2009-07-08 | 有限会社アプライドダイヤモンド | Diamond thin film modification method, diamond thin film modification and thin film formation method, and diamond thin film processing method |
| US6191399B1 (en) | 2000-02-01 | 2001-02-20 | Asm America, Inc. | System of controlling the temperature of a processing chamber |
| US6596973B1 (en) | 2002-03-07 | 2003-07-22 | Asm America, Inc. | Pyrometer calibrated wafer temperature estimator |
| US6818864B2 (en) | 2002-08-09 | 2004-11-16 | Asm America, Inc. | LED heat lamp arrays for CVD heating |
| DE10239486A1 (en) * | 2002-08-21 | 2004-03-04 | Carl Zeiss Smt Ag | Production of a substrate for producing light conducting light glass rods used in illumination systems, involves preparing a substrate molded blank and coating a surface which corresponds to a first substrate outer surface |
| US6976782B1 (en) * | 2003-11-24 | 2005-12-20 | Lam Research Corporation | Methods and apparatus for in situ substrate temperature monitoring |
| US7833581B2 (en) * | 2006-09-11 | 2010-11-16 | The Hong Kong University Of Science And Technology | Method for making a highly stable diamond film on a substrate |
| US9885123B2 (en) | 2011-03-16 | 2018-02-06 | Asm America, Inc. | Rapid bake of semiconductor substrate with upper linear heating elements perpendicular to horizontal gas flow |
| US20220267893A1 (en) * | 2019-11-11 | 2022-08-25 | Beijing Naura Microelectronics Equipment Co., Ltd. | Sputtering device |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53106626A (en) * | 1977-03-02 | 1978-09-16 | Komatsu Mfg Co Ltd | Method of making high purity rod silicon and appratus therefor |
| US4796562A (en) * | 1985-12-03 | 1989-01-10 | Varian Associates, Inc. | Rapid thermal cvd apparatus |
-
1990
- 1990-08-17 US US07/568,857 patent/US5225245A/en not_active Expired - Fee Related
- 1990-08-21 EP EP90116005A patent/EP0436070B1/en not_active Expired - Lifetime
- 1990-08-21 CA CA002023684A patent/CA2023684A1/en not_active Abandoned
- 1990-08-21 DE DE69016633T patent/DE69016633T2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| EP0436070B1 (en) | 1995-02-01 |
| EP0436070A1 (en) | 1991-07-10 |
| DE69016633D1 (en) | 1995-03-16 |
| US5225245A (en) | 1993-07-06 |
| DE69016633T2 (en) | 1995-05-24 |
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| EEER | Examination request | ||
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