|Publication number||US20050026432 A1|
|Application number||US 10/784,586|
|Publication date||Feb 3, 2005|
|Filing date||Feb 23, 2004|
|Priority date||Apr 17, 2001|
|Also published as||US7341927, US20050142879|
|Publication number||10784586, 784586, US 2005/0026432 A1, US 2005/026432 A1, US 20050026432 A1, US 20050026432A1, US 2005026432 A1, US 2005026432A1, US-A1-20050026432, US-A1-2005026432, US2005/0026432A1, US2005/026432A1, US20050026432 A1, US20050026432A1, US2005026432 A1, US2005026432A1|
|Inventors||Harry Atwater, James Zahler, Anna Morral|
|Original Assignee||Atwater Harry A., Zahler James M., Morral Anna Fontcubertai|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (47), Referenced by (28), Classifications (24), Legal Events (1)|
|External Links: USPTO, USPTO Assignment, Espacenet|
The present application is related to U.S. Provisional Application Ser. No. 60/526,332, filed on Dec. 2, 2003 and is a continuation-in-part application related under 35 USC 120 to copending U.S. patent application Ser. No. 10/761,918 filed on Jan. 20, 2004 which in turn was a continuation-in-part application of application Ser. No. 10/125,133 filed on Apr. 17, 2002, and which in turned claimed priority to U.S. Provisional Patent Application Ser. No. 60/284,726, filed on Apr. 17, 2001 which claimed priority pursuant to 35 USC 119, each which related applications are incorporated herein by reference.
1. Field of the Invention
The invention relates to the field of semiconductor processing of films and in particular to processing nonsilicon films on heterostructures.
2. Description of the Prior Art
The optoelectronics, photovoltaics, telecommunications, and LED industries have a need for a substrate technology that allows them to use a low-cost readily available substrate like Si as a mechanical support for a thin film of optoelectronic material on which to fabricate a device. Some obvious advantages are improved mechanical strength and superior thermal conductivity relative to a bulk optoelectronic material.
Group III-V semiconductor layered structures grown on bulk germanium substrates have been used in the prior art to create high efficiency triple-junction solar cells with efficiencies greater than 30%. However, these are prohibitively expensive for all but space applications, because the Ge substrate constitutes a large portion of this cost.
The optoelectronics, photovoltaics, telecommunications, and LED industries would benefit from adopting a substrate technology that allows them to use a low-cost readily available substrate like Si as a mechanical support for a thin film of optoelectronic nonsilicon material on which to fabricate a device. Some obvious advantages are improved mechanical strength and superior thermal conductivity relative to a bulk optoelectronic material.
The invention is an improvement in a method of epitaxially growing heterostructures on a virtual substrate comprised of an optoelectronic device substrate and handle substrate. The method comprises the step of initiating bonding of the device substrate to the handle substrate. The device substrate is composed of a material suitable for fabrication of optoelectronic devices therein and the handle substrate is composed of an inexpensive material suitable for providing mechanical support. The mechanical strength of the device and handle substrates is improved. The device substrate is thinned to leave a single-crystal film on the virtual substrate such as by exfoliation of a device film from the device substrate. An upper portion of the device film exfoliated from the device substrate is removed to provide a smoother and less defect prone surface for subsequent optoelectronic device fabrication. The heterostructure is epitaxially grown on the smoothed surface.
In the illustrated embodiment the device substrate is InP/Si and the step of epitaxially growing the heterostructure on the smoothed surface comprises the step of epitaxially growing a photoluminescent InP/InGaAs/InP double heterostructure on the smoothed surface.
The step of removing an upper portion of the device film exfoliated from the device substrate comprises chemically polishing the upper portion with a damage selective etch, or mechanically polishing the upper portion.
Where the device and handle substrates present a InP/Si interface, the chemically polishing the upper portion with a damage selective etch comprises the step of etching with a mixture of HCl:H3PO4:H2O2 used in ratios of 1:2:2 or 1:2:4.
In another embodiment the step of mechanically polishing the upper portion comprises using a colloidal silica slurry in a sodium hypochlorite solution.
The invention is also defined as an improvement in a heterostructure device layer which is epitaxially grown on a virtual substrate. The improvement comprises a device substrate and a handle substrate from which the virtual substrate is formed. The device substrate is bonded to the handle substrate and is composed of a material suitable for fabrication of optoelectronic devices. The handle substrate is composed of a material suitable for providing mechanical support. The mechanical strength of the device and handle substrates is improved and the device substrate is thinned to leave a single-crystal film on the virtual substrate such as by exfoliation of a device film from the device substrate. An upper portion of the device film exfoliated from the device substrate is removed to provide a smoother and less defect prone surface for an optoelectronic device. A heterostructure is epitaxially grown on the smoothed surface in which an optoelectronic device may be fabricated.
While the apparatus and method has or will be described for the sake of grammatical fluidity with functional explanations, it is to be expressly understood that the claims, unless expressly formulated under 35 USC 112, are not to be construed as necessarily limited in any way by the construction of “means” or “steps” limitations, but are to be accorded the full scope of the meaning and equivalents of the definition provided by the claims under the judicial doctrine of equivalents, and in the case where the claims are expressly formulated under 35 USC 112 are to be accorded full statutory equivalents under 35 USC 112. The invention can be better visualized by turning now to the following drawings wherein like elements are referenced by like numerals.
The invention and its various embodiments can now be better understood by turning to the following detailed description of the preferred embodiments which are presented as illustrated examples of the invention defined in the claims. It is expressly understood that the invention as defined by the claims may be broader than the illustrated embodiments described below.
The fabrication 104 of virtual wafer bonded substrates could take two possible approaches as diagrammatically illustrated in the block diagram of
This specification summarizes a number of embodiments of the fabrication of optoelectronic virtual substrates. We begin with a summary of the technology generally employed and device structures for which the virtual substrate product can be used. Next, more material process steps are described in the order that they appear in the fabrication process.
Process And Product Overview
For the purpose of the specification the term “device substrate” 10 is the optoelectronic substrate from which a thin film 12 will be removed. The term “handle substrate” 14 is defined in the specification to refer to the substrate that is used as a mechanical support for the device film 12, namely the remainder of device substrate 10 after removal of film 12. The term “virtual substrate” 16 is defined to be the completed structure of a thin device film 12 on a handle substrate 14.
The materials of interest for device substrate 10 for the discussion below can be considered all materials that are relevant to wafer bonded virtual substrate device film materials for opto-electronic, high-gain device fabrication as diagrammatically illustrated diagrammatically in
The handle substrate 14 will generally be Si, which is abundantly available and has desirable electrical, mechanical, and thermal properties. Hence, a heterostructure with Si can be made according to the teachings and spirit of the invention with any of the materials in the preceding paragraph. However, low-cost insulating substrates (i.e. glass, sapphire, etc.) might also be employed as handle substrate 14.
A generic process for fabricating such virtual substrates 16 comprises the following steps:
1) The device substrate 10 and handle substrate 14 may need pre-bonding treatment to allow the removal of a thin film 12 (i.e. ion-implantation as diagrammatically depicted in
2) The device substrate 10 is cleaned and/or passivated to facilitate bonding.
3) Bonding is initiated as diagrammatically shown in
4) The bond is strengthened to improve the mechanical strength of the device substrate 10 and handle substrate 14.
5) The device substrate 10 is thinned to leave a single-crystal film 12 on the finished virtual substrate 16 as shown in
6) In the case of ion implantation induced layer exfoliation, the device substrate 10 from which the device film 12 was derived can be reprocessed by a means of surface polishing to allow the reuse of the substrate 10 to transfer another device film as illustrated in
Consider the concepts used for the fabrication of optoelectronic virtual substrates 16. These will be listed in the order in which they would appear in the generic process described above.
1) Ion Implantation
Prior to bonding, ion implantation of the device substrate 10 is performed to inject a necessary amount of gas species into the substrate to form the internally passivated surfaces and internal pressure necessary to exfoliate a layer from the substrate upon annealing as diagrammatically depicted in
This process is generally performed with H+ or a combination of H+ and He+. However, other gas species may be employed to produce an intra-substrate etch process to assist in the exfoliation of the layer. For a given device substrate material there is both a minimum implantation temperature to avoid amorphization and a needed implantation temperature, namely a minimum required dose relationship for this process.
a. H+ Implantation—A sufficient dose of H+ is implanted to allow film exfoliation upon annealing. This dose is a function of:
b. H+/He+ Co-implantation—A sufficient total dose of H+ and He+ is implanted to allow film exfoliation upon annealing. The concept of this approach being that the H plays a chemical role of passivating internal surfaces, while the chemically inert He efficiently migrates to internal surfaces to provide pressure, and creates more damage per implanted ion than H increasing the internal surface density. The necessary dose is a function of:
c. Etchant implantation—In addition to or replacement of H+ implantation, chemical species known to etch a given material can be implanted to create internally trapped chemical species that are volatile and cause exfoliation upon annealing. The chemical species chosen will be material specific according to known etchant properties or empirical experience.
2) Surface Passivation
Following implantation and prior to bonding, it is necessary to passivate the surface of both the device and handle substrates 10, 14 to allow hydrophobic wafer bonding. The specific chemical process necessary is device substrate specific. The purpose of this step is to enable the formation of an intimate covalent bond between the device film 12 and handle substrate 14 in the finished virtual substrate 16 allowing for the possibility of ohmic, low-resistance interface electrical properties. A necessary step in enabling this finished device structure will be the elimination of adsorbed water on the surface by means of a low temperature bake in an inert atmosphere or in vacuum. The bake should reach a temperature such that the vapor pressure of water at that temperature is well below the partial pressure of water in the surrounding ambient.
a. Group IV Passivation—The Group IV elemental semiconductors, particularly Ge, are rendered hydrophobic by the use of a dilute HF etching process. This leaves a predominantly hydride terminated surface.
b. Group III/V Passivation—The Group III/V compound semiconductors can be rendered hydrophobic by compound-specific chemical treatments to leave a hydrophobically passivated surface for bonding.
c. Group II/VI Passivation—The Group II/VI compound semiconductors can be rendered hydrophobic by compound-specific chemical treatments to leave a hydrophobically passivated surface for bonding.
d. Ferroelectric Oxides—Applications involving ferroelectric oxides are fundamentally different than those for the optoelectronic materials from the elemental and compound semiconductors. For this reason handle substrate materials will be chosen for their electrical and refractive properties, but there will generally be no need to attempt hydrophobic wafer bonding to the insulating ferroelectric thin films. Thus, surface passivation will generally focus on forming a thin oxide on both the device and handle substrates 10, 14.
3) Surface Modification
Another enabling technology for extending this process to a wide range of optoelectronic materials is the use of a deposited surface modification layer 18 of arbitrary thickness to change the nature of the physical interaction between the substrates 10, 14 as depicted in
a. Deposition of a layer 18 of material X on the device substrate 10 to enable an X-handle material bond.
b. Deposition of a layer 18 of material X on the handle substrate 14 to enable an X-device material bond.
c. Deposition of a layer 18 of material X on both substrates to enable an X-X bond.
This technology enables the integration of a wide range of optoelectronic materials by mastering bonding with a material which is compatible or amendable to the disclosed process, which for the moment is referenced simply as material X. The generic process is illustrated in
More specific applications of this technique are:
d. Epitaxial Si bonding layer—This technique involves epitaxially growing a strained thin film of Si on the device substrate material. In this embodiment material X is strained thin film Si. Through doing this an intimate and maximally strong bond can be ensured between the device material and the Si epitaxial layer. The device substrate 10 with the strained Si epitaxy is then implanted through the epitaxial layer (not shown) in preparation for wafer bonding and layer exfoliation. For material systems utilizing Si handle substrates 14 this would allow direct Si—Si wafer bonding using well established passivation techniques.
e. Amorphous Si bonding layer—This technique involves depositing a thin layer of amorphous Si (not shown) at low temperature on the device substrate 10 to enable the use of typical Si surface preparation chemistries. In this embodiment material X is amorphous Si. This process could be performed either prior to or after ion implantation of the device substrate 10. For material systems utilizing Si handle substrates 14 this would allow direct Si-Si wafer bonding using well established passivation techniques.
4) Particle Removal
Following surface passivation, it may be necessary to remove residual particle contamination on the bonding surfaces of the device and handle substrates 10 and 14. This has been efficiently done by performing a clean with a CO2 particle jet 20 as depicted in
This has been demonstrated for Si, Ge, and InP by maintaining the substrates at a temperature greater than 50° C. during application of the CO2.
5) Elevated Temperature Bond Initiation
When bonding dissimilar materials there is generally a coefficient of thermal expansion mismatch between the two materials resulting in a temperature-dependent strain state of the device thin film 12 in the virtual substrate 16 that is governed by the equation
Such that positive values of strain indicate a film in tension and negative values of strain indicate a film in compression.
6) Dissimilar Temperature Bond Initiation
For some desired engineered stain states, no single elevated bond temperature will enable the fabrication of that device. Likewise, for materials with very similar coefficients of thermal expansion strain engineering will be difficult. To further enable control of strain at a desired temperature, bonding could be initiated between substrates held at different temperatures. In this way, the thermo-mechanical strain state could be more freely controlled or artificially built into the finished structure. In this case the temperature dependent strain state is given by
In this expression, Td and Th are the temperatures of the device substrate 10 and the handle substrate 14 respectively at the instant of bond initiation. The temperature T0 is the effective bond initiation temperature. The dissimilar temperatures of the substrates at bond initiation make this term difficult to determine. T0 must have a value between Td and Th and will depend upon the experimental apparatus used in fabrication of the virtual substrate 16 and can be determined experimentally. The built-in strain approaches
7) Annealing Under Pressure to Strengthen Bonding and Exfoliate the Device Layer—
After the device and handle substrates 10, 14 have been bonded, it is necessary to use a thermal cycle to improve bond strength and to activate the ion implantation layer transfer process. By performing this cycle under pressure, thermo-mechanical strain can be accommodated in the bonded bulk substrate stack. Additionally, bonding is strengthened by means of improved substrate-substrate contact. A bonding process using multiple pressure-temperature steps or even a continuously varying pressure-temperature curve can be used to optimize the effectiveness of pressure in the process.
Specifically, at lower temperatures prior to exfoliation, higher pressures can be employed to ensure better substrate-substrate contact, but these pressures would at higher temperatures subdue exfoliation. By reducing the pressure to a lower level prior to annealing to high temperatures, exfoliation is uninhibited.
a. Variable Pressure Cycle—One possible embodiment is to utilize independently varied pressure and temperature to optimize the bonding process. At low temperatures, high pressures are applied to strengthen the bond. At high temperatures the pressure is then reduced to avoid the suppression of layer exfoliation in the device substrate. A representative process is illustrated in the graph of
b. Single Pressure Cycle—The bonding process is also improved by applying a uni-axial load to the bonded pair for the duration of the anneal. In this process it is essential that the load be small enough to avoid the suppression of blistering.
8) Device Layer Modification
Following the transfer of the device layer 10 in the ion implantation induced layer transfer process, the near surface region of the device film 12 is both rough and defect rich. This layer must be controllably removed to leave a surface that is useful for subsequent processing to fabricate an optoelectronic device as shown in
9) Epitaxial Heterostructure Growth
The finished virtual substrate 16 is meant to serve as a template for growth of an optoelectronic device through hetero-epitaxy. Through careful device layer modification, epitaxy of a wide range of optoelectronic devices is made possible. A representative image of such a structure is shown in
10) Strain Compensation Layer
One potential challenge in implementing wafer bonded virtual substrates in the fabrication of devices in or on the transferred layer by standard processing such as MOCVD, diffusion, implantation, and lithography is the possibility of wafer bow due to the presence of thermal expansion derived strain in the transferred layer. A practical approach to minimizing this effect would be to deposit a strain compensation layer on the back surface of the handle substrate 14 as shown in
This concept would be implemented by depositing a thin film 18 on the back surface of the handle substrate 14 either prior to or after the transfer of the device layer 10 to the handle substrate 14. The strain compensation layer 18 must have the same sign of Δα relative to the handle substrate as the device film 12. The zero bow condition is not a zero strain condition, but rather a condition in which the strain energy of the device film 12 and the strain compensation layer 18 are exactly matched providing no driving force for substrate deformation. The material and deposition technique can be chosen to minimize the fabrication cost associated with this processing step. The strain energy associated with a thin film 12 is increased with substrate diameter, film strain, and film thickness. The strain compensation layer material 18, deposition temperature, and thickness can be chosen to tailor the zero bow process temperature. The following are examples of how strain compensation could be performed for several materials systems:
a. Ge/Si—The simplest case would be to deposit a film of Ge on the back surface of the Si handle substrate.
b. InP/Si—Rather than deposit InP on the back of the handle, a thin film of Ge could be utilized because of its ease of deposition.
c. GaAs/Si—As in the InP/Si case, Ge would make a good strain compensation layer.
d. Other Materials—For all of the systems mentioned above, a low-cost material that is easily deposited is a suitable strain compensation layer, provided that the sign of Δα is appropriate.
Many alterations and modifications may be made by those having ordinary skill in the art without departing from the spirit and scope of the invention. Therefore, it must be understood that the illustrated embodiment has been set forth only for the purposes of example and that it should not be taken as limiting the invention as defined by the following claims. For example, notwithstanding the fact that the elements of a claim are set forth below in a certain combination, it must be expressly understood that the invention includes other combinations of fewer, more or different elements, which are disclosed in above even when not initially claimed in such combinations.
The words used in this specification to describe the invention and its various embodiments are to be understood not only in the sense of their commonly defined meanings, but to include by special definition in this specification structure, material or acts beyond the scope of the commonly defined meanings. Thus if an element can be understood in the context of this specification as including more than one meaning, then its use in a claim must be understood as being generic to all possible meanings supported by the specification and by the word itself.
The definitions of the words or elements of the following claims are, therefore, defined in this specification to include not only the combination of elements which are literally set forth, but all equivalent structure, material or acts for performing substantially the same function in substantially the same way to obtain substantially the same result. In this sense it is therefore contemplated that an equivalent substitution of two or more elements may be made for any one of the elements in the claims below or that a single element may be substituted for two or more elements in a claim. Although elements may be described above as acting in certain combinations and even initially claimed as such, it is to be expressly understood that one or more elements from a claimed combination can in some cases be excised from the combination and that the claimed combination may be directed to a subcombination or variation of a subcombination.
Insubstantial changes from the claimed subject matter as viewed by a person with ordinary skill in the art, now known or later devised, are expressly contemplated as being equivalently within the scope of the claims. Therefore, obvious substitutions now or later known to one with ordinary skill in the art are defined to be within the scope of the defined elements.
The claims are thus to be understood to include what is specifically illustrated and described above, what is conceptionally equivalent, what can be obviously substituted and also what essentially incorporates the essential idea of the invention.
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|International Classification||H01L21/302, H01L31/072, H01L31/109, H01L31/0328, H01L21/461, H01L31/0336|
|Cooperative Classification||H01L21/30625, H01L21/187, Y02E10/50, H01L21/30612, H01L21/76254, H01L31/0392, H01L33/005, H01L21/30604, H01L31/18|
|European Classification||H01L21/18B2, H01L31/18, H01L31/0392, H01L21/762D8B, H01L21/306P, H01L21/306B, H01L21/306B4, H01L33/00G|
|Oct 12, 2004||AS||Assignment|
Owner name: CALIFORNIA INSTITUTE OF TECHNOLOGY, CALIFORNIA
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:ATWATER, HARRY A.;ZAHLER, JAMES;I MORRAL, ANNA FONTCUBERA;REEL/FRAME:015238/0111;SIGNING DATES FROM 20041006 TO 20041009