WO2008023639A1 - Semiconductor substrate for epitaxial growth and process for producing the same - Google Patents
Semiconductor substrate for epitaxial growth and process for producing the same Download PDFInfo
- Publication number
- WO2008023639A1 WO2008023639A1 PCT/JP2007/066014 JP2007066014W WO2008023639A1 WO 2008023639 A1 WO2008023639 A1 WO 2008023639A1 JP 2007066014 W JP2007066014 W JP 2007066014W WO 2008023639 A1 WO2008023639 A1 WO 2008023639A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- substrate
- epitaxial growth
- film
- hgcdte
- cdte
- 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.)
- Ceased
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
- C30B29/48—AIIBVI compounds wherein A is Zn, Cd or Hg, and B is S, Se or Te
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
Definitions
- the present invention relates to an epitaxial growth semiconductor substrate suitable for epitaxial growth of an HgCdTe film and a method for manufacturing the same, and more particularly to a CdTe substrate or a CdZnTe substrate.
- an infrared sensor for detecting infrared rays for example, a pn junction diode obtained by epitaxially growing a HgCdTe film on a CdTe compound semiconductor substrate such as a CdTe substrate or a CdZnTe substrate is known as a photodiode. It has been.
- the growth substrate for epitaxially growing the HgCdTe film is mirror-finished by the method described in Patent Document 1, for example.
- the CdTe substrate for epitaxial growth is obtained by slicing a thin CdTe single crystal obtained by the vertical Bridgman method and other methods, lapping it, and then passing through steps such as etching and polishing.
- the final polishing is performed to finish the wafer surface to a mirror finish. Examples of the final polishing include a mirror etching method and a mirror polishing method.
- Patent Document 1 proposes a mirror-polishing liquid suitable for the mirror-polishing method, whereby a mirror surface with less undulation and less surface abnormality can be obtained.
- an epitaxial growth substrate that has been mirror-finished by the above-described method is not used immediately for epitaxial growth, but may be used for epitaxial growth after being stored for a predetermined period. Many. At this time, the epitaxial growth substrate needs to be kept in a state of being accommodated in a wafer storage container one by one because it is necessary to keep the surface clean.
- Patent Document 2 discloses a wafer storage container suitable for storing an epitaxial growth substrate.
- the wafer storage container storing the wafer is laminated. Wrap it in a bag, and then evacuate the inside of the laminate bag and fill it with an inert gas such as nitrogen gas. Prevent particles from entering the wafer storage container from the unit!
- an oxide film that prevents normal epitaxy growth is formed in many ways.
- an epitaxial film is used in order to remove the oxide film. Etching with Br methanol is performed as a pretreatment for growth.
- Patent Document 1 Japanese Patent Publication No. 6-92278
- Patent Document 2 WO2005 / 112106Al
- the etching process as a pretreatment for the epitaxial growth is time-consuming and the etching process itself deteriorates the quality of the substrate surface, so that the epitaxially grown film formed on the substrate is deteriorated. There is a problem of increasing defects.
- the present invention provides an epitaxial growth semiconductor substrate that does not require an etching process as a pretreatment when performing an epitaxial growth of an HgCdTe film, thereby preventing defects in the HgCdTe growth film.
- the purpose is to reduce.
- the present invention has been made to solve the above-described problem, and is a CdTe-based compound semiconductor substrate for performing HgCdTe epitaxial growth, and within a predetermined time after being subjected to a mirror finish. It is characterized in that the ratio of Te oxide to the total amount of Te contained in the inert gas atmosphere and obtained by XPS measurement is 30% or less. In particular, it is an epitaxial growth substrate made of CdTe or CdZnTe.
- the “total Te amount” means the total amount of Te alone and the Te compound.
- the “mirror finishing process” is a finishing process that is finally performed after the substrate is subjected to a polishing / cleaning process, and is performed by, for example, a mirror polishing method or a mirror etching method.
- an epitaxial growth substrate is accommodated in a predetermined wafer storage container, the wafer storage container is packaged in a laminate bag, and further laminated. and evacuating the bag was filled with nitrogen gas, there s equipotent method for sealing the laminated bag.
- the substrate is accommodated in an inert gas atmosphere within 10 hours. I tried to do it. Thereby, the ratio of Te oxide to the total amount of Te on the substrate surface by XPS measurement can be within the above-mentioned range.
- the inventors of the present invention have formed the surface of the substrate during storage under the view that it is not preferable to perform an etching process as a pretreatment when the HgCdTe film is epitaxially grown on the CdTe substrate. We thought that a good quality epitaxial growth film could be formed without performing an etching process by reducing the oxide film.
- Te oxide accounted for the total amount of Te on the substrate surface measured by XPS. If the ratio of fluoride (Te oxide / total Te) is within 30%, defects generated in the HgCdTe growth film can be effectively reduced.
- the relationship between the time during which the CdTe substrate is exposed to the atmosphere and the amount of the surface oxide film is investigated, and the amount of oxide film formed on the substrate surface is controlled by controlling the time during which the CdTe substrate is exposed to the atmosphere. It was found that it can be controlled. Furthermore, by storing and storing the mirror-finished CdTe substrate in a nitrogen gas atmosphere, the oxide film (Te oxide) on the substrate surface is stored during storage. Since it is possible to avoid the progress of the formation, pay attention to the time until the mirror-finished substrate is accommodated in the nitrogen gas atmosphere, and the Te oxide formed on the CdTe substrate surface by controlling this time Established a method to control the amount of.
- Table 1 shows the time until the mirror-finished CdTe substrate is accommodated in a nitrogen gas atmosphere, and the ratio (%) of Te oxide to the total amount of Te when the CdTe substrate surface is measured by XPS. Show. The XPS measurement of the CdTe substrate surface was performed after storing the mirror-finished CdTe substrate in a nitrogen gas atmosphere for 30 days.
- Te oxide amount / total Te amount increases as the time from mirror finishing to storage in the nitrogen gas atmosphere increases. It can be seen that the formation of Te oxide is in progress. Specifically, the amount of Te oxide / total Te increases gradually when the time from mirror finish to storage in a nitrogen gas atmosphere is 5 minutes, 15 minutes, 60 minutes, 180 minutes, and 600 minutes. The amount of Te oxide / total Te is 45% per day, and the amount of Te oxide / total Te is 80% or more after 30 days or more and is almost saturated.
- the ratio of Te oxide to the total amount of Te on the surface of the CdTe substrate (Te oxide amount / total Te amount) is within 30%, defects generated in the HgCdTe growth film can be effectively reduced.
- After mirror-finishing the substrate, storing it in a nitrogen gas atmosphere within 600 minutes (10 hours) can greatly reduce the effect of the surface oxide film of the CdTe substrate stored in that state on HgCdTe epitaxial growth.
- the present invention has been completed on the basis of the above findings, and is a CdTe system in which the ratio of Te oxide (Te oxide amount / total Te amount) to the total Te amount on the substrate surface is within 30%. It is a compound semiconductor substrate.
- the substrate should be mirror-finished and stored in a nitrogen gas atmosphere within 10 hours! /. The invention's effect
- a CdTe-based semiconductor substrate for example, a CdTe substrate or a CdZnTe substrate
- an oxide film formed on the substrate surface after mirror finishing that is, Te Since the amount of oxide is controlled within 30% of the total amount of Te, defects generated in the epitaxially grown film can be effectively reduced.
- the conventional etching process can be omitted, and the surface of the substrate accompanying the etching process can be omitted. It is possible to prevent the deterioration of quality and the occurrence of defects after epitaxial growth.
- CdTe single crystals were grown by the vertical Bridgman method, which was conventionally used as a CdTe single crystal growth method. Then, the Cd Te substrate thinly cut from the obtained CdTe single crystal was subjected to a polishing / cleaning process such as lapping, etching and polishing, and then subjected to a mirror finishing process by a final polishing process.
- This mirror finishing process is disclosed in, for example, Japanese Patent Application Laid-Open No. 62-290135.
- the mirror-finished CdTe substrate thus obtained was stored in a predetermined wafer storage container and stored for a predetermined period. Thereafter, the CdTe substrate was taken out from the wafer storage container, and an HgCdTe film was epitaxially grown on the substrate.
- the mirror-finished CdTe substrate described above was stored in a wafer storage container and stored in the atmosphere for 180 minutes or 600 minutes, and then stored in a nitrogen gas atmosphere.
- a wafer storage container containing a CdTe substrate was packed in a laminate bag, and the laminate bag was evacuated and then filled with nitrogen gas, and the laminate bag was sealed and placed in a nitrogen gas atmosphere. Tsuma The time from mirror finish to sealing the laminated bag is 180 minutes or 600 minutes.
- the CdTe substrate was taken out from the wafer storage container, and an HgCdTe film was epitaxially grown on the substrate (without etching treatment as a pretreatment).
- Table 2 shows the amount of Te oxide / total Te on the surface of the CdTe substrate and the number of defects generated in the HgCdTe growth film.
- the Te oxide amount / total Te amount on the CdTe substrate surface is calculated from the total Te amount and Te oxide amount when the CdTe substrate surface is measured by XPS.
- the number of defects in the HgCdTe growth film is indicated by the density calculated from the number of defects that can be seen in the field of view by observing the surface of the growth film with an optical microscope (X200).
- the amount of Te oxide / total Te on the surface of the CdTe substrate before epitaxial growth was 30% or less, so an extremely good HgCdTe film with a small number of defects generated in the HgCdTe growth film was formed. I was able to grow it.
- Comparative Example 1 the above-described mirror-finished CdTe substrate was stored in a wafer storage container and stored in the atmosphere for 1, 30, or 120 days, and then stored in a nitrogen gas atmosphere.
- the accommodation method in a nitrogen gas atmosphere is the same as in the example.
- Table 3 shows the amount of Te oxide / total amount of Te on the surface of the CdTe substrate and the number of defects generated in the HgCdTe growth film.
- the amount of Te oxide / total Te was 45% and the number of defects generated in the HgCdTe growth film was 1700 / cm 2 when housed in a nitrogen gas atmosphere within one day after mirror finishing. .
- the amount of Te oxide / total Te was 82%, and the number of defects generated in the HgCdTe growth film was 3350 / cm 2 .
- the Te oxide amount / total Te amount was 80%, and the number of defects generated in the HgCdTe growth film was 3100 / cm 2 .
- Comparative Example 2 the mirror-finished CdTe substrate described above was stored in a wafer storage container and stored in the atmosphere for 30 days. Thereafter, the CdTe substrate was taken out from the wafer storage container, and the substrate was etched with Br methanol, and then the HgCdTe film was epitaxially grown.
- Table 4 shows the number of defects generated in the HgCdTe growth film. From Table 4, when the mirror-finished CdTe substrate was stored in the air, the number of defects generated in the HgCdTe growth film was 2300 / cm.
- the Te oxide film formed on the substrate surface was removed, but the surface quality deteriorated. Therefore, the number of defects generated in the HgCdTe growth film has increased. Compared with the results of the examples, the number of defects in the HgCdTe growth film is about five times. Compared with the results of Comparative Example 1, the number of defects in the HgCdTe growth film can be reduced by etching with Br methanol when stored in the atmosphere for 30 days or more. It can be seen that if the period is about one day, the number of defects in the HgCdTe growth film is reduced without the Br methanol etching process.
- the HgCdTe film is more than the case of performing the pretreatment etching process.
- the number of defects generated in the growth film can be significantly reduced.
- it is desirable that the time from when the CdTe substrate is mirror-finished to being accommodated in the nitrogen gas atmosphere is 10 hours or less.
- the present invention is not limited to the above-described embodiments, but can be modified without departing from the gist thereof.
- the force described in the case of using a CdTe single crystal as a substrate is also effective when other CdTe-based compound semiconductor single crystals (for example, CdZnTe single crystals) are used as substrates for epitaxial growth.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Light Receiving Elements (AREA)
Description
Claims
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP07792631.9A EP2055814B1 (en) | 2006-08-25 | 2007-08-17 | Process for producing a semiconductor substrate for epitaxial growth |
| US12/438,636 US7875957B2 (en) | 2006-08-25 | 2007-08-17 | Semiconductor substrate for epitaxial growth and manufacturing method thereof |
| JP2008530885A JP5234963B2 (ja) | 2006-08-25 | 2007-08-17 | エピタキシャル成長用半導体基板の製造方法 |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006229171 | 2006-08-25 | ||
| JP2006-229171 | 2006-08-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2008023639A1 true WO2008023639A1 (en) | 2008-02-28 |
Family
ID=39106724
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2007/066014 Ceased WO2008023639A1 (en) | 2006-08-25 | 2007-08-17 | Semiconductor substrate for epitaxial growth and process for producing the same |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US7875957B2 (ja) |
| EP (1) | EP2055814B1 (ja) |
| JP (1) | JP5234963B2 (ja) |
| WO (1) | WO2008023639A1 (ja) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011040566A1 (ja) * | 2009-09-30 | 2011-04-07 | Jx日鉱日石金属株式会社 | エピタキシャル成長用CdTe系半導体基板及び基板収納物 |
| JP2011124417A (ja) * | 2009-12-11 | 2011-06-23 | Jx Nippon Mining & Metals Corp | CdTe系半導体基板の製造方法及びCdTe系半導体基板 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2977372B1 (fr) * | 2011-06-30 | 2015-12-18 | Soc Fr Detecteurs Infrarouges Sofradir | Procede pour la realisation d'un detecteur de rayonnement electro-magnetique et detecteur obtenu par ce procede |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60215600A (ja) * | 1984-04-09 | 1985-10-28 | Nec Corp | Hg↓1↓−xCdxTe結晶の製造方法 |
| JPS62290135A (ja) * | 1986-06-10 | 1987-12-17 | Nippon Mining Co Ltd | CdTeウェーハの鏡面研磨液ならびに鏡面研磨方法 |
| JPS6321300A (ja) * | 1986-07-16 | 1988-01-28 | Nippon Mining Co Ltd | エピタキシヤル成長基板用CdTe単結晶及びその製造方法 |
| JPH02239188A (ja) * | 1989-03-09 | 1990-09-21 | Nippon Mining Co Ltd | エピタキシャル成長方法 |
| JPH0692278A (ja) | 1992-09-11 | 1994-04-05 | Mazda Motor Corp | 車両シートの搭載装置 |
| JPH06125148A (ja) * | 1992-10-09 | 1994-05-06 | Sumitomo Metal Mining Co Ltd | 低抵抗半導体結晶基板及びその製造方法 |
| JPH06345598A (ja) * | 1993-06-04 | 1994-12-20 | Japan Energy Corp | 放射線検出素子用CdTe結晶およびその製造方法 |
| WO2005112106A1 (ja) | 2004-05-19 | 2005-11-24 | Nippon Mining & Metals Co., Ltd. | ウェハ保管容器 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4487640A (en) * | 1983-02-22 | 1984-12-11 | The United States Of America As Represented By The Secretary Of The Air Force | Method for the preparation of epitaxial films of mercury cadmium telluride |
| US4648917A (en) * | 1985-08-26 | 1987-03-10 | Ford Aerospace & Communications Corporation | Non isothermal method for epitaxially growing HgCdTe |
| JPS62213133A (ja) * | 1986-03-13 | 1987-09-19 | Fujitsu Ltd | 半導体結晶成長方法 |
-
2007
- 2007-08-17 EP EP07792631.9A patent/EP2055814B1/en active Active
- 2007-08-17 JP JP2008530885A patent/JP5234963B2/ja active Active
- 2007-08-17 US US12/438,636 patent/US7875957B2/en active Active
- 2007-08-17 WO PCT/JP2007/066014 patent/WO2008023639A1/ja not_active Ceased
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60215600A (ja) * | 1984-04-09 | 1985-10-28 | Nec Corp | Hg↓1↓−xCdxTe結晶の製造方法 |
| JPS62290135A (ja) * | 1986-06-10 | 1987-12-17 | Nippon Mining Co Ltd | CdTeウェーハの鏡面研磨液ならびに鏡面研磨方法 |
| JPS6321300A (ja) * | 1986-07-16 | 1988-01-28 | Nippon Mining Co Ltd | エピタキシヤル成長基板用CdTe単結晶及びその製造方法 |
| JPH02239188A (ja) * | 1989-03-09 | 1990-09-21 | Nippon Mining Co Ltd | エピタキシャル成長方法 |
| JPH0692278A (ja) | 1992-09-11 | 1994-04-05 | Mazda Motor Corp | 車両シートの搭載装置 |
| JPH06125148A (ja) * | 1992-10-09 | 1994-05-06 | Sumitomo Metal Mining Co Ltd | 低抵抗半導体結晶基板及びその製造方法 |
| JPH06345598A (ja) * | 1993-06-04 | 1994-12-20 | Japan Energy Corp | 放射線検出素子用CdTe結晶およびその製造方法 |
| WO2005112106A1 (ja) | 2004-05-19 | 2005-11-24 | Nippon Mining & Metals Co., Ltd. | ウェハ保管容器 |
Non-Patent Citations (1)
| Title |
|---|
| ERNE B.H. ET AL.: "Surface films on HgCdTe and CdTe etched in ferricyanide solution", APPLIED SURFACE SCIENCE, vol. 175-176, 15 May 2001 (2001-05-15), pages 579 - 584, XP003021219 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011040566A1 (ja) * | 2009-09-30 | 2011-04-07 | Jx日鉱日石金属株式会社 | エピタキシャル成長用CdTe系半導体基板及び基板収納物 |
| US8513775B2 (en) | 2009-09-30 | 2013-08-20 | Jx Nippon Mining & Metals Corporation | CdTe semiconductor substrate for epitaxial growth and substrate container |
| JP5449381B2 (ja) * | 2009-09-30 | 2014-03-19 | Jx日鉱日石金属株式会社 | エピタキシャル成長用CdTe系半導体基板、基板の保管方法及びエピタキシャル成長方法 |
| JP2011124417A (ja) * | 2009-12-11 | 2011-06-23 | Jx Nippon Mining & Metals Corp | CdTe系半導体基板の製造方法及びCdTe系半導体基板 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2055814A4 (en) | 2013-09-25 |
| EP2055814A1 (en) | 2009-05-06 |
| EP2055814B1 (en) | 2018-08-08 |
| US7875957B2 (en) | 2011-01-25 |
| JP5234963B2 (ja) | 2013-07-10 |
| JPWO2008023639A1 (ja) | 2010-01-07 |
| US20090269271A1 (en) | 2009-10-29 |
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