WO2007147184A2 - Verfahren zum herstellen von photoaktiven schichten sowie bauelemente umfassend diese schicht(en) - Google Patents
Verfahren zum herstellen von photoaktiven schichten sowie bauelemente umfassend diese schicht(en) Download PDFInfo
- Publication number
- WO2007147184A2 WO2007147184A2 PCT/AT2007/000296 AT2007000296W WO2007147184A2 WO 2007147184 A2 WO2007147184 A2 WO 2007147184A2 AT 2007000296 W AT2007000296 W AT 2007000296W WO 2007147184 A2 WO2007147184 A2 WO 2007147184A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- layer
- semiconductive
- metal compound
- metal
- semiconducting
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
- H10F77/00—Constructional details of devices covered by this subclass
- H10F77/10—Semiconductor bodies
- H10F77/12—Active materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
- H10F77/00—Constructional details of devices covered by this subclass
- H10F77/10—Semiconductor bodies
- H10F77/12—Active materials
- H10F77/126—Active materials comprising only Group I-III-VI chalcopyrite materials, e.g. CuInSe2, CuGaSe2 or CuInGaSe2 [CIGS]
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
- H10F71/00—Manufacture or treatment of devices covered by this subclass
- H10F71/125—The active layers comprising only Group II-VI materials, e.g. CdS, ZnS or CdTe
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/541—CuInSe2 material PV cells
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/543—Solar cells from Group II-VI materials
-
- 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
Definitions
- the invention relates to a method for producing photoactive layers and to components comprising this layer (s).
- Semiconducting metal sulfides, selenides and tellurides are important materials for the formation of photoactive layers, which are useful, inter alia, for photovoltaic applications.
- semiconducting metal sulfides in the form of thin layers are used for inorganic solar cells, so-called ETA cells (Extreme Thin Absorber Cells).
- ETA cells Extreme Thin Absorber Cells.
- a method for producing a Kupferindiumsulfidkomplexes at low temperatures describe Castro, Bailey et al. 1301 .
- relatively expensive starting compounds are used according to this method.
- the present invention is therefore based on the object to provide a simple Kunststoffbuchs method for the preparation of photoactive layers, which can be carried out on the one hand at low temperatures and on the other hand with the direct use of easily synthesized Metallverbmditch and reactants.
- a method of the type mentioned is proposed, which is characterized in that from precursor material comprising at least one metal compound and a salt-like and / or organic reactants on a substrate by printing or knife coating, a non-semiconductive layer is formed, which temperatures of less than 300 0 C is exposed, wherein from the non-semiconducting layer by thermal conversion of the precursor material, a semiconductive, photoactive layer is formed.
- a non-semiconductive material consisting of a metal compound, such as metal salts and / or metal complexes, and a salt-like or organic compound which releases in the conversion step, a further necessary for the semiconductor component.
- the invention further relates to components, such as solar cells or photodetectors, which comprise the layers produced according to the invention.
- the reaction temperature of the decomposition reaction may be advantageously well below 300 0 C, especially if the reaction is catalyzed by an acid or base, and / or acidic or alkaline starting compounds are used.
- the conversion takes place in the presence of a Lewis base, for example pyridine.
- Lewis bases act as Complexing agent for the metal ions used.
- Lewis bases play a crucial role in the decomposition reaction of the reactant, for example in the preparation of chalcogenides with thioacetamide as sulfur source.
- Lewis bases are F “ , OH “ , O 2 “ , H 2 O, NH 3 and its derivatives, Br “ , N 3 “ , NO 2 “ , I ⁇ , S 2 , SCN. "
- Lewis used bases are especially nitrogen-containing organic bases, such as pyridine and / or derivatives of pyridine, various primary, secondary and / or tertiary amines, nitrogen-containing heterocycles, deprotonated amino acids and / or bases with a pyrimidine skeleton.
- reaction conditions can be chosen such that the semiconductors are present in the layer in nanocrystalline form or as nanoparticles.
- the mixture of the starting substances can be present both in solution and as a slurry (slurry), as a dispersion or as a paste.
- metal compounds which can react with a salt-like or organic reaction partner are used as semiconductor particles.
- the metal compound (s) serving as the starting compound (s) may also be a salt-like compound.
- the metal compound may be an organometallic compound or an organometallic complex.
- the metal compound (s) used may have both basic and acidic properties that allow for conversion at lower temperatures or catalytically affect the conversion.
- a high current efficiency of the components in the form of solar cells is achieved in that the inorganic materials are particles whose grain size is preferably between 0.5 nm and 500 nm.
- the semiconducting layers according to the invention can assume the role of the electron donor as well as of the electron acceptor in solar cells.
- the transition temperature in a semiconductor may also be below 100 0 C.
- the conversion of the starting compounds into semiconductors can be carried out in the presence of an acid.
- the conversion of the starting compounds into semiconductors can likewise advantageously be carried out in the presence of a base.
- the reaction temperature can be adjusted by thermal treatment but also by photons with an energy greater than 1 (a) eV.
- the application is carried out by printing with known printing methods, such as flexographic printing or gravure printing, or by Aufräkeln of the semiconductor on the substrate.
- Example 1 Process for the preparation of semiconducting copper-indium sulfide layers The preparation of copper indium sulfide layers takes place by reaction of thioacetamide as sulfur-containing reaction partner in the presence of a copper and indium salt, whereby thioacetamide is decomposed.
- InCl 3 and CuI are complexed in pyridine.
- Thiourea is dissolved in this solution.
- This reaction solution is applied to a suitable substrate, such as indium tin oxide on glass, an organic polymer or an electroactive organic polymer, by dripping and heated to 200 0 C under an inert gas atmosphere (eg, nitrogen, argon, helium).
- Cu x (pyridines) y + I "
- Example 2 Production of an inorganic / organic hybrid solar cell: The basic structure of this hybrid solar cell is shown in FIG.
- the carrier 1 is a glass substrate or a transparent polymer film.
- part of the ITO layer (indium / tin oxide layer) 2 is removed by chemical or physical etching.
- a polyethylene dioxythiophene (PEDOT: PSS) layer 3 In order to compensate for the roughness of the layer, it is optionally possible to apply a polyethylene dioxythiophene (PEDOT: PSS) layer 3. However, this step can be omitted.
- a layer 4 of an organic electroactive polymer or a low molecular weight organic electroactive substance is applied. Preferably be from polymer solutions • 'suspensions or homogeneous solutions by spin coating, dip coating, knife coating, printing or spraying applied. Low molecular weight substances can also be vapor-deposited.
- a CuInS 2 layer is then prepared as prepared according to Example 1 (layer 5).
- the electrodes 6 such as aluminum, Gold, silver, or a combination of calcite alpha / gold, calcium / aluminum, magnesium / gold deposited by vapor deposition or sputtering.
- Example 3 Process for the preparation of semiconducting zinc sulphide layers
- the preparation of the zinc sulfide layers is carried out by decomposition of thioacetamide in the presence of zinc acetate.
- the decomposition was carried out in this case at 150 ° C.
- the X-ray diffractogram in FIG. 4 shows the nanocrystalline ZnS phase formed. Sphalerite was identified as a crystallographic phase. The width of the reflections confirms the presence of primary crystallites in the nanometer range.
- a bilayer heterojunction solar cell As an application for such a layer, a bilayer heterojunction solar cell was realized whose efficiencies were characterized by means of a U / I characteristic curve (see FIG. 5). The solar cell produced in this way shows a particularly high photovoltage of 920 mV.
- Example 4 Process for Producing a CuGaS 2 Layer
- 31.5 mg of CuI, 37.9 mg of GaCl 3 and 64.5 mg of thioacetamide are dissolved in pyridine and applied to a glass substrate.
- This layer is heated under inert gas atmosphere for 30 min at 200 0 C wherein the conversion is carried out in a CuGaS 2 layer.
- FIG. 6 shows a diffractogram of the nanocrystalline semiconductor layer formed, the peaks characteristic for the CuGaS 2 being 29 °, 48 °, 49 ° and 57 °.
- the sharp peaks at 24 °, 25.5 °, 27.5 °, 42 °, 46.5 ° and 50 ° come from small amounts of the reactant CuI, which was not fully implemented. By increasing the gallium component these Eduktpeaks can be eliminated.
- Example 5 Method for producing a copper-iron sulfide layer
- Example 6 Process for producing a silver-gallium sulfide layer
- S-compounds can also be used: elemental sulfur, elemental sulfur and a vulcanization accelerator, thiourea, thiuram, hydrogen sulfide, metal sulfides, hydrogen sulfides, CS 2 , P 2 S 5 ;
- metal thiocarbamide compounds can be used.
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- Photovoltaic Devices (AREA)
- Compounds Of Iron (AREA)
Abstract
Description
Claims
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BRPI0713494-0A BRPI0713494A2 (pt) | 2006-06-22 | 2007-06-18 | método para a produção de camadas fotoativas e componentes que compreendam a(s) referida(s) camadas(s) |
| MX2008016100A MX2008016100A (es) | 2006-06-22 | 2007-06-18 | Proceso para la produccion de capas fotoactivas asi como componentes que comprenden una o varias de estas capas. |
| EP07718505A EP2030245A2 (de) | 2006-06-22 | 2007-06-18 | Verfahren zum herstellen von photoaktiven schichten sowie bauelemente umfassend diese schichten |
| CA002654588A CA2654588A1 (en) | 2006-06-22 | 2007-06-18 | Method for producing photoactive layers and components comprising said layer(s) |
| JP2009515669A JP2009541976A (ja) | 2006-06-22 | 2007-06-18 | 光活性層及び1又は複数の該層を含んでなる構成部品の製法 |
| US12/306,136 US20090235978A1 (en) | 2006-06-22 | 2007-06-18 | Method for producing photoactive layers and componets comprising said layer(s) |
| CN2007800234746A CN101479853B (zh) | 2006-06-22 | 2007-06-18 | 制备光活性层的方法以及包含这样的层的器件 |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ATA1058/2006 | 2006-06-22 | ||
| AT0105806A AT503837B1 (de) | 2006-06-22 | 2006-06-22 | Verfahren zum herstellen von photoaktiven schichten sowie bauelemente umfassend diese schicht(en) |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| WO2007147184A2 true WO2007147184A2 (de) | 2007-12-27 |
| WO2007147184A3 WO2007147184A3 (de) | 2008-04-24 |
Family
ID=38833780
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/AT2007/000296 Ceased WO2007147184A2 (de) | 2006-06-22 | 2007-06-18 | Verfahren zum herstellen von photoaktiven schichten sowie bauelemente umfassend diese schicht(en) |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US20090235978A1 (de) |
| EP (1) | EP2030245A2 (de) |
| JP (1) | JP2009541976A (de) |
| KR (1) | KR20090039708A (de) |
| CN (1) | CN101479853B (de) |
| AT (1) | AT503837B1 (de) |
| BR (1) | BRPI0713494A2 (de) |
| CA (1) | CA2654588A1 (de) |
| MX (1) | MX2008016100A (de) |
| WO (1) | WO2007147184A2 (de) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010087205A (ja) * | 2008-09-30 | 2010-04-15 | Kaneka Corp | 多接合型薄膜光電変換装置 |
| JP2010129658A (ja) * | 2008-11-26 | 2010-06-10 | Kyocera Corp | 化合物半導体薄膜の製法および薄膜太陽電池の製法 |
| JP2010129659A (ja) * | 2008-11-26 | 2010-06-10 | Kyocera Corp | 化合物半導体薄膜の製法および薄膜太陽電池の製法 |
| JP2010232256A (ja) * | 2009-03-26 | 2010-10-14 | Kyocera Corp | 薄膜太陽電池の製法 |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5464984B2 (ja) * | 2009-11-26 | 2014-04-09 | 京セラ株式会社 | 半導体層の製造方法および光電変換装置の製造方法 |
| JP5495849B2 (ja) * | 2010-02-25 | 2014-05-21 | 京セラ株式会社 | 半導体層の製造方法および光電変換装置の製造方法 |
| KR20130034662A (ko) * | 2010-06-29 | 2013-04-05 | 메르크 파텐트 게엠베하 | 반도체막의 제조 |
| WO2014196311A1 (ja) * | 2013-06-03 | 2014-12-11 | 東京応化工業株式会社 | 錯体およびその溶液の製造方法、太陽電池用光吸収層の製造方法および太陽電池の製造方法 |
| JP6259685B2 (ja) * | 2013-10-03 | 2018-01-10 | 積水化学工業株式会社 | 半導体形成用塗布液、半導体薄膜、薄膜太陽電池及び薄膜太陽電池の製造方法 |
| CN109545981A (zh) * | 2018-11-27 | 2019-03-29 | 江苏拓正茂源新能源有限公司 | 一种有机太阳能电池及其制备方法 |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE621339A (de) * | 1961-08-30 | 1900-01-01 | ||
| US4095006A (en) * | 1976-03-26 | 1978-06-13 | Photon Power, Inc. | Cadmium sulfide film |
| GB9123684D0 (en) * | 1991-11-07 | 1992-01-02 | Bp Solar Ltd | Ohmic contacts |
| US5920798A (en) * | 1996-05-28 | 1999-07-06 | Matsushita Battery Industrial Co., Ltd. | Method of preparing a semiconductor layer for an optical transforming device |
| DE69734183T8 (de) * | 1996-10-15 | 2007-03-29 | Matsushita Electric Industrial Co., Ltd., Kadoma | Sonnenzelle und Herstellungsverfahren |
| US6537845B1 (en) * | 2001-08-30 | 2003-03-25 | Mccandless Brian E. | Chemical surface deposition of ultra-thin semiconductors |
| US7468146B2 (en) * | 2002-09-12 | 2008-12-23 | Agfa-Gevaert | Metal chalcogenide composite nano-particles and layers therewith |
| US20060057766A1 (en) * | 2003-07-08 | 2006-03-16 | Quanxi Jia | Method for preparation of semiconductive films |
| US7163835B2 (en) * | 2003-09-26 | 2007-01-16 | E. I. Du Pont De Nemours And Company | Method for producing thin semiconductor films by deposition from solution |
| CH697007A5 (fr) * | 2004-05-03 | 2008-03-14 | Solaronix Sa | Procédé pour produire un composé chalcopyrite en couche mince. |
| US20050271827A1 (en) * | 2004-06-07 | 2005-12-08 | Malle Krunks | Solar cell based on CulnS2 absorber layer prepared by chemical spray pyrolysis |
-
2006
- 2006-06-22 AT AT0105806A patent/AT503837B1/de not_active IP Right Cessation
-
2007
- 2007-06-18 CN CN2007800234746A patent/CN101479853B/zh not_active Expired - Fee Related
- 2007-06-18 WO PCT/AT2007/000296 patent/WO2007147184A2/de not_active Ceased
- 2007-06-18 EP EP07718505A patent/EP2030245A2/de not_active Withdrawn
- 2007-06-18 MX MX2008016100A patent/MX2008016100A/es active IP Right Grant
- 2007-06-18 BR BRPI0713494-0A patent/BRPI0713494A2/pt not_active IP Right Cessation
- 2007-06-18 KR KR1020097000311A patent/KR20090039708A/ko not_active Withdrawn
- 2007-06-18 JP JP2009515669A patent/JP2009541976A/ja active Pending
- 2007-06-18 CA CA002654588A patent/CA2654588A1/en not_active Abandoned
- 2007-06-18 US US12/306,136 patent/US20090235978A1/en not_active Abandoned
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010087205A (ja) * | 2008-09-30 | 2010-04-15 | Kaneka Corp | 多接合型薄膜光電変換装置 |
| JP2010129658A (ja) * | 2008-11-26 | 2010-06-10 | Kyocera Corp | 化合物半導体薄膜の製法および薄膜太陽電池の製法 |
| JP2010129659A (ja) * | 2008-11-26 | 2010-06-10 | Kyocera Corp | 化合物半導体薄膜の製法および薄膜太陽電池の製法 |
| JP2010232256A (ja) * | 2009-03-26 | 2010-10-14 | Kyocera Corp | 薄膜太陽電池の製法 |
Also Published As
| Publication number | Publication date |
|---|---|
| MX2008016100A (es) | 2009-01-15 |
| AT503837A1 (de) | 2008-01-15 |
| WO2007147184A3 (de) | 2008-04-24 |
| AT503837B1 (de) | 2009-01-15 |
| KR20090039708A (ko) | 2009-04-22 |
| CN101479853A (zh) | 2009-07-08 |
| BRPI0713494A2 (pt) | 2012-01-24 |
| US20090235978A1 (en) | 2009-09-24 |
| CA2654588A1 (en) | 2007-12-27 |
| JP2009541976A (ja) | 2009-11-26 |
| CN101479853B (zh) | 2013-01-02 |
| EP2030245A2 (de) | 2009-03-04 |
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