GB2342226A - Growing a deuterium containing insulation layer - Google Patents

Growing a deuterium containing insulation layer Download PDF

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Publication number
GB2342226A
GB2342226A GB9922758A GB9922758A GB2342226A GB 2342226 A GB2342226 A GB 2342226A GB 9922758 A GB9922758 A GB 9922758A GB 9922758 A GB9922758 A GB 9922758A GB 2342226 A GB2342226 A GB 2342226A
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United Kingdom
Prior art keywords
insulation film
semiconductor device
furnace
forming
deuterium
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.)
Withdrawn
Application number
GB9922758A
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GB9922758D0 (en
Inventor
Hyun Sang Hwang
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Gwangju Institute of Science and Technology
SK Hynix Inc
Original Assignee
Gwangju Institute of Science and Technology
Hyundai Electronics Industries Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Gwangju Institute of Science and Technology, Hyundai Electronics Industries Co Ltd filed Critical Gwangju Institute of Science and Technology
Publication of GB9922758D0 publication Critical patent/GB9922758D0/en
Publication of GB2342226A publication Critical patent/GB2342226A/en
Withdrawn legal-status Critical Current

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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02107Forming insulating materials on a substrate
    • H01L21/02225Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/02227Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process
    • H01L21/0223Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate
    • H01L21/02233Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate of the semiconductor substrate or a semiconductor layer
    • H01L21/02236Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate of the semiconductor substrate or a semiconductor layer group IV semiconductor
    • H01L21/02238Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate of the semiconductor substrate or a semiconductor layer group IV semiconductor silicon in uncombined form, i.e. pure silicon
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02107Forming insulating materials on a substrate
    • H01L21/02109Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/02164Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material being a silicon oxide, e.g. SiO2
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02107Forming insulating materials on a substrate
    • H01L21/02225Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/02227Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process
    • H01L21/02255Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by thermal treatment

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Formation Of Insulating Films (AREA)
  • Insulated Gate Type Field-Effect Transistor (AREA)

Abstract

An oxide or oxynitride layer is grown on a silicon substrate in a deuterium containing atmosphere in a furnace. The insulation layer may be grown in a deuterium oxide atmosphere. The layer may have a multilayer structure with a conventional insulating layer either overlying or underlying the deuterium oxide/oxynitride layer. The atmosphere in the furnace may be purely deuterium oxide or have a conventional oxidising gas component (ie oxygen, nitrogen monoxide or nitrogen dioxide). The leakage and breakdown characteristics of the insulation film are improved due to the formation of strong silicon-deuterium bonds.

Description

2342226 l\l[ETHOD OF FORMING AN INSXJLATION F11LM IN A SEMICONDUCTOR
DEVICE
FIELD OF THE INVENTION
1. Field of the Invention
71he present invention relates to a method of forming an insulation film that is an essential process in manufacturing a Metal Oxide Semiconductor (MOS), which can be applicable to all the Ultra Large Scale Integration (ULSI) to which MOS is applied.
2. Description of the Prior Art
In a conventional technology, to form an insulation Elm such as a gate oxide, a S'02 insulation film is formed on a silicon wafer by annealing the silicon wafer at high temperature in the ambient of oxygen, hydrogen or steam. The Si02 insulation film is contained a large amount of hydrogen, whereby Si-H bonds are created in SiO2 insulation film.
As the degree of integration of the semiconductor device is increased, the thickness of the insulation film is scaled less than 50A. As the thickness of the insulation film becomes scaled, the Si-H bonds easy to break by an electrical stress. Thus, it may cause a problem in which an electrical and reliability characteristics of the insulation film such as a lowered WDB (time-independent 1 dielectric breakdown) characteristics and an increased SILC (Stress induced leakage current), etc.
In order to obtain a higher integration of the semiconductor device, it is required that the insulation film must be very thin and uniform while keeping a good reliability characteristics. However, as explained above, the conventional technology has a limitation.
According to a paper called Results of Improved Device Reliability Using Deuterium (D2) on'IEEE Electron Device Letter, Vol. 18, No. 3, March p. 81-83, 199T, it is said that, in a final step after manufacturing of the device, an annealing C> process is performed under the ambient of deuterium (D2) so that any silicon dangling bonds that are not combined with oxides existing at a Si/si02 interface have the strong bond force of Si-D instead of conventional SPH bond, thereby the electrical and reliability characteristics of the insulation film becomes relatively good even though a high electrical field is applied to it during operation of the device. However, in case of depositing a Si3N4 layer VAth a passivation layer, this method has a problem that it does not greatly improve the device characteristics since a Si-D bond is difficult to Gonn at Si/Si02 interface due to difficulty of difflusion of deuterium (Q) throm-fli the Si3N4 layer. Also, this method has a problem that it could not add a stiff'icicnt amount of deuterium (D2) to the interface because the temperature during the diermal process could not be set higher than the melting point of aluminum used as a metal wire.
2 S LTAINIARY OF TBE E-N3NTIO It is therefore an object of the present invention to provide a method of forming an insulation film in a semiconductor device, capable of solving the above problems by improve the electrical and reliability characteristics of the device by which an insulation film is directly grown in the ambient of deuterium oxide (D20)or deuterium (D2) so that deuterium can be easily added to aSi/Si02 interface.
BRIEF DESCRIPTION OF TBE DRAWING
The above object, and other features and advantages of the present invention will become more apparent by describing the preferred embodiment thereof with reference to the accompanying drawing, in which:
Fig. 1 shows a graph for illustrating the phenomenon in which electrons are trapped into an insulation film in a MOS capacitor.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENT
During the process of manufacturing a semiconductor device, a method of forming an insulation film such as a gate oxide is essential. As the integration of the semiconductor device becomes higher, the thickness of the insulation film is scaled less than 50A and the electrical reliability characteristics has to be also improved.
To improve the electrical reliability characteristics of the insulation film, the method performs an oxidizing process using deuterium oxide (D20) or deuterium(D2) to so that deuterium can be easily added to theSi/S'02 interface. In other words, the present invention makes a Si-D bond be formed at the Si/Si02 interface during the process of forming the insulation film.
Meanwhile, as in the following Example 2 and 3, the oxidizing temperature of the first and second steps can be controlled to a proper range. In other words, the oxidizing temperature of the first and second steps is proceeded simultaneously or differently, so that the thickness of the insulation and the containing amount of deuterium can be controlled independently.
A preferred embodiment of the present invention will be explained below in detail by reference to the accompanying drawing.
<Example l>
After cleaning a silicon wafer on which an insulation film will be fonned, the silicon wafer is loaded into a furnace which is heated to at the temperature of 650 through 750 C. Then, deuterium oxygen (D20) is supplied into it at the temperature of 750 through 1,050 C to fonii aii insulation film on the silicon wafer, thus completing a semicondtictor de- .,,,ice.
In the above Example 1, deutenum oxide i, supplied at the flow rate of 3 through 10 SLM (standard liter per minute).
4 <Example 2>
As in Example 1, after the silicon wafer is loaded into the furnace, at a first Step 02 is supplied into it at the flow rate of 3 through 10 SLM to grow a first insulation film having the thickness of 30 through 50A on the silicon wafer, and at a second step deuterium oxide is supplied into it at the flow rate of 3 through 10 SLM to grow a second insulation film having the thickness of 10 through 3 OA on the first insulation firm, thus completing an insulation film according to the present invention, wherein02being an oxidizing gas and deuterium oxide (D20) are used respectively at the temperature of 750 through 1,050 C In the above Example 2, NO or N02 may be used instead of 02 used in the first step, and also the fast and second step may be changed in order.
<Example 3>
As in Example 1, after the silicon wafer is loaded into the furnace, at a first step deuterium oxygen is supplied into it at the flow rate of 3 through 10 SLM at the temperature of 750 through 950 'C to grow a first insulation film having the thickness of 30 through 50A on the silicon wafer, and at a second step NO or N02 is supplied into it at the flow rate of 3 SLM through 10 at the temperature of 95 0 through 1,050 C to grow a second insulation film having the thickness of 10 through 30A on the first insulation firm, thus completing an insulation film C> according to the present invention, wherein NO or NO, being oxidizing gases and Z deuterium oxygen (D20) are used respectively.
In the above Example 3, 0-, being an oxidizing gas may be used instead of No or N02 used in the second step, and also the first and second step may be changed in order. Also, deuterium oxygen may be used in the second step and NO or N02 may be used in the first step, without varying the temperature.
<Example 4>
As in Example 1, after the silicon wafer is loaded into the furnace, NO or N02 being oxidizing gases and deuterium oxygen (D20) are used simultaneously at the temperature of 750 through 1,050 'C and the combined gases are supplied into it at the flow rate of 3 through 1 OSLM, thus forming an insulation film on the silicon wafer. At this time, the combined ratio of NO or N02 to deuterium oxygen is 1: 0. 1 through 10.
In the above Example 4, 02 being an oxidizing gas may be used instead of No or N02.
<Example 5>
As in Example 1, after the silicon wafer is loaded into the furnace, 02being an oxidizing gas and deuterium (D2) are used si ii i t 11 tmeously at the temperature of 750 through 1,050 'C and the combined gases are upplied into it at the flow rate of 3 through 10SLM, thus forming aii insulation filin on the silicon wafer. At this time, the combined ratioOf 02to deuterium (D,,) Is 1: 0.5 through 2.
In the above Example 5, 02 being an oxidiz-iiig gas may be used instead of C> -A x i 6 No or N02.
With the above examples, deuterium is added at the Si/Si02 interface to form a Si-D bond. Further, the fi=ace to which these examples may be applied include both a tube-type furnace and a rapid then-nal furnace.
<Test Example> Fig. 1 shows the phenomenon AVc; resulting from trapped electrons into C) respective insulation films of a MOS capacitor in which an insulation film of 17nm is grown by using deuterium oxide (D20) and H20 at the temperature of 900 'C. In Fig. 1, AVG represents a gate voltage shift under constant current, which was 10 MA/CM2 in this test example. As can be seen from Fig. 1, comparing the insulation film grown under the ambient of conventional H20 and the insulation film which is groAm under the ambient of D20. the amount of trapped electrons is dr-amatically decreased in the insulation film grown under the ambient of D20 than that under the ambient of H.,O. Therefore, it can be seen that the device reliability is high in the insulation film grown under the ambient of D20 than that under the ambient of H20.
As described above, the present invention can improve the electrical reliability characteristics of a device by growing an insulation film under the ambient of deuterium oxide or deuterium so that a sufficient amount of deuterium 7 can be added to aSi/Si02 interface. Therefore, the insulation film accordina to W the present invention has not only a good electrical reliability, but also can easily add deuterium into the Si/Si02 interface regardless a passivation layer of by controlling the amount of deuterium existing at the insulation film.
While the present invention has been described and illustrated herein with reference to the preferred embodiment thereof, it ',XAII be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention.
8

Claims (23)

M7HAT IS CLAIMEED IS:
1 A method of fom-iing an insulation film in a semiconductor device, comprising the steps of. cleaning a silicon wafer and then loading the silicon wafer into a furnace; and growing an insulation film on the silicon wafer by supplying a deuterium oxide into said furnace.
2. The method of fom-iing an insulation film in a semiconductor device as claimed in Claim 1, wherein said loading temperature is 650 through 750 C and the growth temperature of said insulation film is 750 through 1,050 'C.
3. The method of forming an insulation film in a semiconductor device as claimed in Claim 1, wherein said deuterium oxide is supplied into said furnace at the flow rate of 3 through 1 OSLM.
4. A method of fom-iing an insulation film in a semiconductor device, comprising the steps of. cleaning a silicon wafer and then loading said silicon wafer into a furnace; growing a first insulation film on said silicon wafer by supplying an oxidizing gas into said furnace; and growing a second insulation film on said first insulation film by supplying 9 deuterium oxide into said furnace, thereby forn-ting an insulation film contained deuterium.
5. The method of forming an insulation film in a semiconductor device as claimed in Claim 4, wherein said oxidizing gas is at least one of 0, NO and N02.
C> -
6. The method of forming an insulation film in a semiconductor device as claimed in Claim 4, wherein the growth temperature of said first and second insulation film is 750 through 1,050 C.
7. The method of forn-fing an insulation fih-n in a semiconductor device as claimed in Claim 4, wherein the growth temperature of said first insulation fLIm is 750 through 950 C, and the growth temperature of said second insulation film is 950 through 1,050 'C.
8. The method of forming an insulation film in a semiconductor device as claimed in Claim 4, wherein said oxidizing gas and said deuterium oxide is C_ respectively supplied into the furnace at the flow n tie of 3 through 1 OSLM.
9. A method of forming an insiiIation ftirn M a semiconductor device, comprising the steps of. cleaning a silicon wafer and then loading s t 1 (.1 silicon wafer into a flirnace; to growing a first insulation film on said silicon wafer by supplying deuterium into said furnace; and growing a second insulation film on said first insulation film by supplying an oxidizing gas into said furnace, thereby forming an insulation film contained deuterium.
10. The method of forming an insulation film in a semiconductor device as claimed in Claim 9, wherein said oxidizing gas is at least one Of 02, NO and N02.
11. The method of forming an insulation film in a sen-ticonductor device as claimed in Claim 9, wherein the growth temperature of said first and second insulation film is 750 through 1,050 C.
12. The method of forming an insulation film in a sen-Liconductor device as claimed in Claim 9, wherein the growth temperature of said first insulation film is 750 through 950 'C, and the growth temperature of said second insulation film is 950 through 1,050 C.
13. The method of forming an insulation filni in a semiconductor device as claimed in Claim 9, wherein said oxidizing gas and said deuterium oxide is C> respectively supplied into the fi=ace at the flow rate of -3) through 1 OSLM.
11
14. A method of fom-fing an insulation film in a semiconductor device, comprising the steps of.
cleaning a silicon wafer and then loading said silicon wafer into a furnace; gTowing an insulation film on said silicon wafer by supplying an oxidizing gas and deuterium oxide into said furnace.
15. The method of fonning an insulation film in a semiconductor device as claimed in Claim 14, wherein said loading temperature is 650 and 750 'C, and the growth temperature of said insulation film is 750 through 1,050 'C.
16. The method of forming an insulation film in a semiconductor device as claimed in Claim 14, wherein said oxidizing gas and said deuterium oxide is respectively supplied into the furnace at the flow rate of 3 through 1 OSLM.
17. The method of forming an insulation film in a semiconductor device as claimed in Claim 14, wherein said oxidizing gas is at least oneOf 02, NO andN02.
18. The method of forming an insulation Illin in a semiconductor device as claimed in Claim 9, in case of using NO or No.,x., oxidizing gas, the combined ratio ofNO or N02to deuterium ox c n s 1. 0, 1 t 11 rough 10.
19. A method of fom-iing an insulation Iffin in a semiconductor device, 12 comprising the steps of. cleaning a silicon wafer and then loading said silicon wafer into a furnace; growing an insulation film on said silicon wafer by supplying an oxidizing gas and deuterium into said furnace.
20. The method of forming an insulation film in a semiconductor device as claimed in Claim 19, wherein said loading temperature is 650 and 750 'C, and the growth temperature of said insulation film is 750 through 1,050 'C.
21. The method of forming an insulation film in a semiconductor device as claimed in Claim 19, wherein said oxidizing gas and said deuterium oxide is respectively supplied into the furnace at the flow rate of 3 through 1 OSLM.
22. The method of forming an insulation film in a semiconductor device as claimed in Claim 19, wherein said oxidizing gas is at least one Of 025 NO and N02.
23. The method of forming an insulation film in a semiconductor device as claimed in Claim 19, in case of using 02 as said oxidizing gas, the combined ratio Of 02 to deuterium is 1 A5 through 2.
13
GB9922758A 1998-09-28 1999-09-27 Growing a deuterium containing insulation layer Withdrawn GB2342226A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
KR1019980040260A KR20000021246A (en) 1998-09-28 1998-09-28 Method for forming insulating film for semiconductor device using deuterium oxide or deuterium

Publications (2)

Publication Number Publication Date
GB9922758D0 GB9922758D0 (en) 1999-11-24
GB2342226A true GB2342226A (en) 2000-04-05

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KR (1) KR20000021246A (en)
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TW (1) TW419745B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107154354A (en) * 2016-03-03 2017-09-12 上海新昇半导体科技有限公司 Wafer heat-treating methods

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100474190B1 (en) * 2000-12-19 2005-03-08 주식회사 하이닉스반도체 Method of thermal process in a semiconductor device
KR100500698B1 (en) * 2002-11-20 2005-07-12 광주과학기술원 Dangling bond decrease Method for forming high-permitivity gate dielectric
JP4999265B2 (en) * 2004-08-27 2012-08-15 大陽日酸株式会社 Method for manufacturing gate insulating film
US7253020B2 (en) 2005-01-04 2007-08-07 Omnivision Technologies, Inc Deuterium alloy process for image sensors

Citations (4)

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Publication number Priority date Publication date Assignee Title
WO1997026676A1 (en) * 1996-01-16 1997-07-24 The Board Of Trustees Of The University Of Illinois Semiconductor devices, and methods for same
WO1997045864A1 (en) * 1996-05-31 1997-12-04 Lam Research Corporation Improved method of polycrystalline silicon hydrogenation
JPH1012609A (en) * 1996-06-21 1998-01-16 Toshiba Corp Semiconductor device and its manufacture
JPH10200115A (en) * 1996-12-27 1998-07-31 Matsushita Electric Ind Co Ltd Thin film transistor and method for manufacturing the same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997026676A1 (en) * 1996-01-16 1997-07-24 The Board Of Trustees Of The University Of Illinois Semiconductor devices, and methods for same
WO1997045864A1 (en) * 1996-05-31 1997-12-04 Lam Research Corporation Improved method of polycrystalline silicon hydrogenation
JPH1012609A (en) * 1996-06-21 1998-01-16 Toshiba Corp Semiconductor device and its manufacture
JPH10200115A (en) * 1996-12-27 1998-07-31 Matsushita Electric Ind Co Ltd Thin film transistor and method for manufacturing the same

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
WPI Abstract Accession No1998-136470 & JP 10 012 609 A *
WPI Abstract Accession No1998-473291 & JP 10 200 115 A *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107154354A (en) * 2016-03-03 2017-09-12 上海新昇半导体科技有限公司 Wafer heat-treating methods
CN107154354B (en) * 2016-03-03 2020-12-11 上海新昇半导体科技有限公司 Method for heat treatment of wafer
DE102016114940B4 (en) 2016-03-03 2023-04-27 Zing Semiconductor Corporation Thermal processing method for a wafer

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Publication number Publication date
GB9922758D0 (en) 1999-11-24
TW419745B (en) 2001-01-21
KR20000021246A (en) 2000-04-25
JP2000150508A (en) 2000-05-30

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