CN101609861B - Manufacturing process for laminated-silicon thin film solar cell - Google Patents
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- CN101609861B CN101609861B CN2009100653986A CN200910065398A CN101609861B CN 101609861 B CN101609861 B CN 101609861B CN 2009100653986 A CN2009100653986 A CN 2009100653986A CN 200910065398 A CN200910065398 A CN 200910065398A CN 101609861 B CN101609861 B CN 101609861B
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 16
- 239000010703 silicon Substances 0.000 title claims abstract description 16
- 239000010409 thin film Substances 0.000 title claims abstract description 16
- 230000001105 regulatory effect Effects 0.000 claims abstract description 3
- 238000000151 deposition Methods 0.000 claims description 52
- 230000008021 deposition Effects 0.000 claims description 49
- KRQUFUKTQHISJB-YYADALCUSA-N 2-[(E)-N-[2-(4-chlorophenoxy)propoxy]-C-propylcarbonimidoyl]-3-hydroxy-5-(thian-3-yl)cyclohex-2-en-1-one Chemical compound CCC\C(=N/OCC(C)OC1=CC=C(Cl)C=C1)C1=C(O)CC(CC1=O)C1CCCSC1 KRQUFUKTQHISJB-YYADALCUSA-N 0.000 claims description 26
- 239000000758 substrate Substances 0.000 claims description 19
- 239000011521 glass Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 4
- 238000005229 chemical vapour deposition Methods 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 abstract description 28
- 239000012159 carrier gas Substances 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 4
- 239000004065 semiconductor Substances 0.000 abstract description 2
- 230000015556 catabolic process Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 abstract 1
- 239000000843 powder Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 26
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 23
- 238000005516 engineering process Methods 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 230000009466 transformation Effects 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000009832 plasma treatment Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical Vapour Deposition (AREA)
Abstract
The invention relates to a manufacturing process for a laminated-silicon thin film solar cell, belonging to the semiconductor field. The process respectively manufactures pl, il, nl, p2, i2, n2 layers with the help of a single-cavity and multi-cavity PECVD system and by regulating technological parameters such as the proportion of deposited gas and carrier gas, discharge powder and the like. The process has simple flow, is easy to be realized; and the laminated-silicon thin film solar cell manufactured by the process has high conversion rate, low light-induced degradation effect, high open circuit voltage and higher filling factors.
Description
One technical field
The present invention relates to a kind of manufacturing process of thin film solar cell, particularly a kind of manufacturing process of silicon-film solar-cell belongs to semiconductor applications.
Two background technologies
The exhaustion day by day of world's fossil energy develops new forms of energy various countries respectively as strategic industry, solar cell is an important branch of utilization of new energy resources, the solar cell technology of ripe main flow is based on monocrystalline silicon and polycrystalline silicon solar cell in the market, but because the environmental problem that exists in the cost limit that the shortage of silicon materials causes and the production crystalline silicon process, the application of crystal-silicon solar cell and development have been subjected to very big constraint, it is few that silicon-film solar-cell has a consumptive material, environmental friendliness, advantages such as cost decline space is bigger, research and production unit one after another with silicon-film solar-cell as research and development principal direction
Silicon-film solar-cell p-i-n type is main, and the subject matter that this silicon-film solar-cell exists is that transformation efficiency is low and photic attenuating effect is higher.For addressing these problems, people have proposed multiple scheme, comprise and make suitable P layer, the interface of interlayer is handled, battery is carried out annealing in process etc. that these The Application of Technology have to a certain degree improvement to the quality of battery, but what improve not obvious especially on transformation efficiency.In order to improve the transformation efficiency of battery, the development laminated cell is an important directions in next period.
Three summary of the invention
The present invention is for providing a kind of manufacturing process of laminated-silicon thin film solar cell.
The manufacturing process of laminated-silicon thin film solar cell provided by the present invention adopts dull and stereotyped appearance formula plasma reinforced chemical vapor deposition system, and the transparent conducting glass substrate is sent into the settling chamber of sealing, comprises step:
A) deposition top anode p1 layer at first feeds SiH4, CH4, B2H6, H2 deposition, closes SiH4, CH4, B2H6 air inlet aura then, opens SiH4 again and deposits.
B) deposition top battery intrinsic layer i1 layer feeds SiH4, H2 deposition.
C) deposition top battery cathode n1 (13) layer is finished in two steps, and the first step feeds SiH
4, PH
3, H
2, earlier at SiH
4With H
2Volume ratio greater than 10% state deposit, close SiH then
4And PH
3Carry out aura, second step was regulated and makes system at SiH
4With H
2Volume ratio less than 7% state deposit.
D) feed SiH4, B2H6, H2, deposition end anode p2 layer, at the concentration ratio of SiH4 and H2 less than 7% state deposit.
E) feed SiH4, H2, deposition end battery intrinsic layer i2 layer, at the concentration ratio of SiH4 and H2 less than 7% state deposit.
F) feed SiH4, PH3, H2, deposition end battery cathode n2 layer.
The volume ratio of SiH4 and H2 is greater than 10% among the step b; Step c finishes the back deposition surface is carried out plasma treatment, deposition surface is carried out the plasma treatment available gas comprise H2, Ar, CO2; Step f deposits under less than 7% state in the volume ratio of SiH4 and H2 earlier, then in the volume ratio of SiH4 and H2 greater than 10% state deposit; Among the step c second step, and steps d, e at deposition pressure greater than carrying out under the 100Pa, second step among the step c and steps d, e deposition pressure are 130Pa-320Pa.Step f finishes the back and makes the metal back electrode layer.
The laminated-silicon thin film solar cell that adopts this technology to make, can effectively improve absorption and the utilization of battery to light, reduce defective and mismatch between the battery median surface, improve the transfer efficiency of the charge carrier of inside battery, improve the transformation efficiency of battery, prolong the useful life of battery, make the low and high problem of photic attenuating effect of silicon thin-film battery transformation efficiency obtain to a certain degree solution.
Four description of drawings
Accompanying drawing laminated cell structural representation of the present invention
Five embodiments
Accompanying drawing is the schematic diagram of the solar cell made of the manufacturing process of laminated-silicon thin film solar cell provided by the present invention, and 51 is direction of illumination, and 41 is transparent conducting glass, and 11 is the p1 layer, 12 is the i1 layer, and 13 is the n1 layer, and 21 is the p2 layer, 22 is the i2 layer, and 23 is the n3 layer, and 31 is the metal back electrode layer.
The dull and stereotyped appearance formula of this process using plasma reinforced chemical vapor deposition system can be realized in single chamber PECVD (plasma reinforced chemical vapour deposition) system, also can realize at the different chamber of multi-cavity chamber PECVD system.
Transparent conducting glass is sent into the settling chamber, be connected with gas input system, vacuum acquiring system, RF aura generation systems in the settling chamber, the frequency of RF is between 13.56MHz-100MHz, and the conductive film of transparent conducting glass can be tin oxide, tin indium oxide, zinc oxide, fluorine doped tin oxide.
Transparent conducting glass is sent into the PECVD system of sealing, and the vacuum acquiring system that utilizes system configuration is evacuated to 10 with the base vacuum of settling chamber
-4More than the Pa, can adopt H2 or Ar gas that system is repeatedly cleaned finds time, heated substrates temperature to 180 ℃-240 ℃, feed deposition gases and carrier gas, calculate and determine the flow of each gas according to volume ratio SiH4: CH4: B2H6: H2=1: 0.4-0.7: 0.006-0.015: 2-6, maintain at system pressure and to carry out aura deposition between the 50Pa-100Pa, glow power calculates at 8mW-300mW/cm according to substrate area
2Between, when the deposition thickness is 10nm to 15nm, close the valve of SiH4, CH4, B2H6, continue aura 5-20 second, open the silane valve, deposition is 20 seconds to 50 seconds when system pressure is kept 50Pa-100Pa, finishes the making of p1 layer.Base vacuum is evacuated to 10
-4More than the Pa, can adopt H2 or Ar gas that system is repeatedly cleaned finds time, heated substrates temperature to 180 ℃-240 ℃, feed deposition gases and carrier gas, calculate the flow that feeds gas according to volume ratio SiH4: H2=1: 1.8-4, maintain at system pressure and to carry out aura deposition between the 70Pa-120Pa, glow power calculates at 8mW-300mW/cm according to substrate area
2Between, when the deposition thickness is between 1500-2500nm, close air intake valve and stop aura, finish the making of i1 layer.Base vacuum is evacuated to 10
-4More than the Pa, can adopt H2 or Ar gas that system is repeatedly cleaned finds time, heated substrates temperature to 180 ℃-240 ℃, feed deposition gases and carrier gas, at first calculate the flow that feeds gas according to volume ratio SiH4: PH3: H2=1: 0.006-0.015: 2-4, maintain at system pressure and to carry out aura deposition between the 70Pa-120Pa, glow power calculates at 8mW-300mW/cm according to substrate area
2, when stopping aura between 5-10nm, the deposition thickness closes air inlet, and can evacuation system vacuum to 10
-4More than the Pa, feeding hydrogen maintains 50Pa-150Pa and carried out aura 5 seconds-15 seconds, also can directly be evacuated to 10
-4More than the Pa, heated substrates temperature to 180 ℃-240 ℃, feed deposition gases and carrier gas, calculate the flow that feeds gas according to volume ratio SiH4: PH3: H2=1: 0.006-0.015: 14.5-25, maintain at system pressure and to carry out aura deposition between the 130Pa-320Pa, glow power calculates at 50mW-500mW/cm according to substrate area
2, when stopping aura between 15-50nm, the deposition thickness closes air inlet, and can select to utilize the H2 aura that deposition surface is carried out plasma treatment, finish the making of n1 layer.System is evacuated to 10
-4More than the Pa, can adopt H2 or Ar gas that system is repeatedly cleaned finds time, heated substrates temperature to 180 ℃-240 ℃, feed deposition gases and carrier gas, calculate the flow that feeds gas according to volume ratio SiH4: B2H6: H2=1: 0.006-0.015: 14.5-25, maintain at system pressure and to carry out aura deposition between the 130Pa-320Pa, glow power calculates at 50mW-500mW/cm according to substrate area
2, when stopping aura between 15-30nm, the deposition thickness closes air inlet, finish the making of p2 layer.System is evacuated to 10
-4More than the Pa, can adopt H2 or Ar gas that system is repeatedly cleaned finds time, heated substrates temperature to 180 ℃-240 ℃, feed deposition gases and carrier gas, calculate the flow that feeds gas than SiH4: H2=1: 14.5-25 according to gas volume, maintain at system pressure and to carry out aura deposition between the 130Pa-320Pa, glow power calculates at 50mW-500mW/cm according to substrate area
2, when stopping aura between 2000-4500nm, the deposition thickness closes air inlet, finish the making of i2 layer.The making of n2 layer can directly be evacuated to 10 with system
-4More than the Pa, can select to adopt H2 or Ar gas that system is repeatedly cleaned finds time, heated substrates temperature to 180 ℃-240 ℃, feed deposition gases and carrier gas, calculate the flow that feeds gas according to volume ratio SiH4: PH3: H2=1: 0.006-0.015: 4-6, maintain at system pressure and to carry out aura deposition between the 80Pa-160Pa, glow power calculates at 10mW-300mW/cm according to substrate area
2, when stopping aura between 20-30nm, the deposition thickness closes air inlet, finish the making of n2 layer.In order to obtain better effect, system can be evacuated to 10
-4More than the Pa, selecting to adopt H2 or Ar gas that system is repeatedly cleaned finds time, heated substrates temperature to 180 ℃-240 ℃, feed deposition gases and carrier gas, at first calculate the flow that feeds gas according to volume ratio SiH4: PH3: H2=1: 0.006-0.015: 14.5-25, maintain at system pressure and to carry out aura deposition between the 130Pa-320Pa, glow power calculates at 50mW-500mW/cm according to substrate area
2, when stopping aura between 10-15nm, the deposition thickness closes air inlet, then system is evacuated to 10
-4More than the Pa, calculate the flow that feeds gas according to volume ratio SiH4: PH3: H2=1: 0.006-0.015: 4-6, maintain at system pressure and carry out the aura deposition between the 80Pa-160Pa, glow power calculates at 10mW-300mW/cm according to substrate area
2, close the making that the n2 layer is finished in air inlet when the deposition thickness stops aura between 10-20nm.Finish after the making of n2 layer, can select to carry out sputter ZnO, make metal back electrode then, metal back electrode can aluminium, also can select other electric conducting material for use, can adopt evaporation, magnetron sputtering or other method to finish the making of metal back electrode.
When utilizing this technology to deposit to make battery, in the aura deposition process, can utilize the vacuum of system configuration to keep system and be bled in the settling chamber, calculate the relative equilibrium that rate of air sucked in required and air inflow keep deposition pressure.
Make efficient for improving, this technology is finished on the multi-cavity chamber system again, can dispose the RF generating means of different frequency on the different chambers.
Claims (6)
1. the manufacturing process of a laminated-silicon thin film solar cell adopts dull and stereotyped appearance formula plasma reinforced chemical vapor deposition system, and the transparent conducting glass substrate is sent into the settling chamber of sealing, may further comprise the steps:
A) deposition top anode p1 (11) layer at first feeds SiH
4, CH
4, B
2H
6, H
2Deposition is closed SiH then
4, CH
4, B
2H
6The air inlet aura is opened SiH again
4Deposit;
B) deposition top battery intrinsic layer i1 (12) layer feeds SiH
4, H
2Deposition;
C) deposition top battery cathode n1 (13) layer is finished in two steps, and the first step feeds SiH
4, PH
3, H
2, earlier at SiH
4With H
2Volume ratio greater than 10% state deposit, close SiH then
4And PH
3Carry out aura, second step was regulated and makes system at SiH
4With H
2Volume ratio less than 7% state deposit;
D) feed SiH
4, B
2H
6, H
2, deposition end anode p2 (21) layer is at SiH
4With H
2Concentration ratio less than 7% state deposit;
E) feed SiH
4, H
2, deposition end battery intrinsic layer i2 (22) layer is at SiH
4With H
2Concentration ratio less than 7% state deposit;
F) feed SiH
4, PH
3, H
2, deposition end battery cathode n2 (23) layer.
2. the manufacturing process of a kind of laminated-silicon thin film solar cell according to claim 1 is characterized in that: SiH among the step b
4With H
2Volume ratio greater than 10%.
3. the manufacturing process of a kind of laminated-silicon thin film solar cell according to claim 1 is characterized in that: step f is earlier at SiH
4With H
2Volume ratio less than depositing under 7% the state, then at SiH
4With H
2Volume ratio greater than 10% state deposit.
4. the manufacturing process of a kind of laminated-silicon thin film solar cell according to claim 1 is characterized in that: second step among the step c and steps d, e at deposition pressure greater than carrying out under the 100Pa.
5. the manufacturing process of a kind of laminated-silicon thin film solar cell according to claim 1, it is characterized in that: second step among the step c and steps d, e deposition pressure are 130-320Pa.
6. the manufacturing process of a kind of laminated-silicon thin film solar cell according to claim 1 is characterized in that: make metal back electrode layer (31) after step f finishes.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100653986A CN101609861B (en) | 2009-06-29 | 2009-06-29 | Manufacturing process for laminated-silicon thin film solar cell |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100653986A CN101609861B (en) | 2009-06-29 | 2009-06-29 | Manufacturing process for laminated-silicon thin film solar cell |
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| Publication Number | Publication Date |
|---|---|
| CN101609861A CN101609861A (en) | 2009-12-23 |
| CN101609861B true CN101609861B (en) | 2010-11-03 |
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|---|---|---|---|
| CN2009100653986A Expired - Fee Related CN101609861B (en) | 2009-06-29 | 2009-06-29 | Manufacturing process for laminated-silicon thin film solar cell |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115287636B (en) * | 2022-07-25 | 2023-11-24 | 中国电子科技集团公司第四十八研究所 | LPCVD pressure control system and pressure control method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6425791B1 (en) * | 1998-06-11 | 2002-07-30 | Micron Technology, Inc. | Method of making a field emission device with buffer layer |
| CN1945952A (en) * | 2006-10-23 | 2007-04-11 | 深圳市拓日电子科技有限公司 | Integrated double junction non-crystal silicon solar energy battery curtain wall and its producing method and use |
-
2009
- 2009-06-29 CN CN2009100653986A patent/CN101609861B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6425791B1 (en) * | 1998-06-11 | 2002-07-30 | Micron Technology, Inc. | Method of making a field emission device with buffer layer |
| CN1945952A (en) * | 2006-10-23 | 2007-04-11 | 深圳市拓日电子科技有限公司 | Integrated double junction non-crystal silicon solar energy battery curtain wall and its producing method and use |
Non-Patent Citations (2)
| Title |
|---|
| JP特开昭61-35570A 1986.02.20 |
| JP特开昭63-244887A 1988.10.12 |
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Inventor after: Wang Hui Inventor after: Hu Juntian Inventor after: Zhao Chunqing Inventor after: Zhao Wenjun Inventor after: Qin Xiaohai Inventor after: Cai Cen Inventor after: Jiao Guoqing Inventor after: Ren Yongping Inventor after: Wang Enzhong Inventor after: Zhang Wenqing Inventor before: Wang Hui Inventor before: Ren Yongping Inventor before: Wang Enzhong Inventor before: Hu Juntian Inventor before: Zhang Wenqing Inventor before: Qin Xiaohai Inventor before: Cai Cen Inventor before: Jiao Guoqing |
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Free format text: CORRECT: INVENTOR; FROM: WANG HUI REN YONGPING WANG ENZHONG HU JUNTIAN ZHANG WENQING QIN XIAOHAI CAI CEN JIAO GUOQING TO: WANG HUI ZHAO CHUNQING ZHAO WENJUN QIN XIAOHAI CAI CEN JIAO GUOQING REN YONGPING WANG ENZHONG ZHANG WENQING HU JUNTIAN |
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Granted publication date: 20101103 Termination date: 20130629 |