CN1317740C - Preparation of SnOz transient layer by high-temperature oxide method - Google Patents
Preparation of SnOz transient layer by high-temperature oxide method Download PDFInfo
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- CN1317740C CN1317740C CNB2004100813802A CN200410081380A CN1317740C CN 1317740 C CN1317740 C CN 1317740C CN B2004100813802 A CNB2004100813802 A CN B2004100813802A CN 200410081380 A CN200410081380 A CN 200410081380A CN 1317740 C CN1317740 C CN 1317740C
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Abstract
The present invention relates to a method for preparing a SnO2 transition layer by a high temperature oxidation method. The SnO2 transition layer belongs to a novel photoelectron material. The method mainly adopts a new manufacture technique, and a transparent intrinsic SnO2 film is formed on a transparent low-resistance SnO2: F thin film by high-temperature oxidation. The SnO2 film is used as a transition layer of a transparent front electrode and a CdS layer, so the short wave response of Cds/CdTe batteries is increased under the condition of thinning the CdS layer, and the transfer efficiency of CdTe solar batteries is increased by 1 to 2%. The method of the present invention simplifies the production technique of the SnO2 transition layer and greatly reduces product cost.
Description
Technical field under in the of one
The field is the sub-material of novel photoelectric under this invention.
Two background technologies
Badeker is in the electrically conducting transparent characteristic of reported first CdO in 1907, and after this, (Transparent Conducting Oxide, TCO) research and application have obtained develop rapidly to transparent conductive film.The TCO film is the pith that constitutes solar cell, LCD, electroluminescent device and multiple photounit and senser element.
The resistivity of TCO film is usually less than 10
-3Ω .cm, visible light transmissivity is greater than 85%.At present, as transparent conductive film material, studying and making with the most use is metal oxide, and SnO is more typically arranged
2: F, ZnO:Al, CdO, In
2O
3, CdIn
2O
4, Cd
2SnO
4, Zn
2SnO
4And In
2O
3: Sn (ITO) etc.Wherein, SnO
2: the F film is stable 600 ℃ of following photoelectric properties, and does not have diode characteristic between the CdS layer, thereby, SnO
2: F is the preferred material of the transparent preceding electrode of CdS/CdTe solar cell.
In II-VI family polycrystalline compounds semiconductor film solar cell, the CdS film forms the pn knot as n type Window layer and p type CdTe material, forms the CdS/CdTe solar cell.The theoretical transformation efficient of this battery can be up to 28%.Present international state-of-the-art is 16.5%, by the breadboard Xu.W initiative of American National regenerative resource.In the CdS/CdTe battery, because the energy gap width of CdS is 2.42eV, the CdS layer can absorb about 30% incident photon in the sunlight, and this partially absorbs the not contribution of conversion efficiency to solar cell.In order to improve the conversion efficiency of CdS/CdTe battery, must as much as possiblely allow incident photon enter into np knot depletion layer, the electronics-hole that produces in the np knot be to can effectively being collected, to opto-electronic conversion as contribution.Therefore, in the measure that improves the CdS/CdTe battery conversion efficiency, reducing the CdS layer thickness is a very effective method.Behind the CdS layer thickness attenuate, the uniformity of film is affected, micropore can occur in film.The micropore of CdS can cause the short circuit of cell p n final result portion again, destroys the pn junction characteristic.In order to solve this contradiction, need be at SnO
2: introduce layer of transparent high resistant transition layer film between F transparent conductive film and the CdS.Through practice, relatively more conventional way is to select the intrinsic material of nesa coating, as the transparency high transition film.As electrically conducting transparent SnO
2: the F film, its high resistant transition zone anthology is levied SnO
2Transparent membrane.For transparent conductive film ZnO:Al, its high resistant buffer layer material anthology is levied ZnO.In addition, Al
2O
3, SiO
2And TiO
2Deng also can be used as the transparency high film.
Select the intrinsic material of transparent conductive film as the high resistant transition zone remarkable advantages to be arranged, it is adaptive to reduce lattice, potential barrier can not occur between transition zone and transparent conductive film, helps the transmission of charge carrier.
Its stock of TCO film is a metal oxide.Metal oxide is under specific preparation condition, be heated or vacuum environment in can lose the partial oxygen atom, the oxygen room appears in the place at the Lattice Oxygen atom, originally and a little less than two electronics quilts of oxygen atom pairing constrain in around the oxygen room, the heat energy of room temperature just can make the electron detachment constraint, free movement in crystal becomes the free movement charge carrier in the lattice.The oxygen room shows as having two positive charges.Following formula is the relational expression of oxygen room and Lattice Oxygen ion and electronics:
V represents the room, and subscript O represents to be in the oxonium ion position in the lattice, mark. and ^ represents positive and negative effective charge.As can be seen, in hot environment, if the oxygen concentration height of film outside, then oxygen atom can diffuse into the oxygen atom in the film to the film diffusion inside from equation, and a part can enter lattice position, fills up the oxygen room; Another part oxygen atom enters calking position or crystal boundary place, increases the crystal boundary potential barrier, reduces the circulation of charge carrier.By changing oxygen ion vacancy number or dopant ion concentration in the film, can both obviously improve the electrical property of thin-film material.
The method for preparing the transparency high transition layer film is a lot, and existing bibliographical information deposits transition zone SnO with radio frequency, magnetically controlled DC sputtering
2, ZnO; Normal pressure, low-pressure chemical vapor deposition (APCVD/LPCVD) and plasma reinforced chemical vapour deposition methods such as (PECVD) deposition SnO
2, the ZnO transition zone.
Three summary of the invention
Purpose of the present invention is to seek a kind of new method and new technology, production large tracts of land, SnO cheaply
2Transition layer film.
In metal oxide body, owing to there is a large amount of oxygen room to exist, n type charge carrier can be contributed in the oxygen room; Mixing of F ion on the other hand, n type charge carrier also can be contributed in the seat of replacement lattice oxygen.If can the oxygen room in the body be compensated, will reduce carrier concentration in the part, low-resistance region is become high resistance area.The present invention utilizes high-temperature oxidation method, at SnO
2: the F surface forms the high resistant transition zone.The method can shorten the production cycle, reduces production costs, and significantly improves CdTe solar cell conversion efficiency.
Its basic principle is: utilizes the relational expression of explaining previously, in the environment of high temperature hyperoxia, allows oxygen atom diffuse into crystal, and oxygen atom room in the compensation film, thus reduce intracrystalline free carrier quantity, increase the resistivity of crystal.Specific practice is with conduction SnO
2: the F film is placed in the container of sealing, and aerating oxygen or oxygen carry hydrogen peroxide or ozone again, and sample is heated to 350-550 ℃, and oxidization time can be selected according to factors such as thickness and required high resistant scopes.
Four embodiments
Embodiment one: with SnO
2: the F film is put into airtight container.The method also can be applied to following film:
ITO, SnO
2: F (Sb, Cl, In, Ni, P), ZnO:Al (F, In, B, Ga), Cd
2SnO
4, Zn
2SnO
4Deng.
Require at high temperature to have seal, guarantee that the work atmosphere of the inside can not leak.Feed purity oxygen.With the air in the pure oxygen eliminating container.Temperature is raised to 500～550 ℃, puts into sample and carries out oxidation.Oxidization time is 10～150 minutes.Oxidated layer thickness was directly proportional with time and temperature.The structure of film does not change through XRD analysis before and after the oxidation.
Embodiment two: with SnO
2: the F film is put into airtight container.SnO
2: the F film can be following film:
ITO, SnO
2: F (Sb, Cl, In, Ni, P), ZnO:Al (F, In, B, Ga), Cd
2SnO
4, Zn
2SnO
4Deng.
Container can be quartz or steel vessel.Require at high temperature to have seal, guarantee that the work atmosphere of the inside can not leak.
Feed purity oxygen, and with purity oxygen as carrying gas, by a container that fills with hydrogen peroxide, oxygen is emerged bottom hydrogen peroxide, makes to carry a large amount of hydrogen peroxide molecules in the oxygen.This oxygen that carries hydrogen peroxide is added in the high-temperature oxidation environment again.Carrying the purpose of hydrogen peroxide, is the oxygen atmosphere that strengthens in the high-temperature oxidation environment.Particularly the oxidizability of hydrogen peroxide is very strong, helps oxonium ion to SnO
2: the diffusion of F film, easier acquisition high resistance film.The same with embodiment one statement, a significant advantage of the method is not have tangible transition interface, can not increase the interior stress of film newly, rete is combined, and helps the transmission of charge carrier.
Can see SnO from embodiment
2: the F film is through the oxidation of high temperature hyperoxia concentration environment, at SnO
2: the F film surface forms SnO
2High resistance film.The transparent low-resistance SnO for preparing with high-temperature oxidation method
2: F film and transparency high SnO
2Film has constituted the structure of laminated film.This complex thin film structure can satisfy the requirement of CdS/CdTe battery to electrode before transparent.Membrane structure and visible light transmissivity be not through changing behind the high-temperature oxydation.Prepare transparency high SnO with high-temperature oxidation method
2Film has that technology is simple, production cost is low; Product quality can be guaranteed, output can be very big; Do not have tangible interface between the composite bed, the adhesion of film is good, does not introduce new defective, helps the transmission of charge carrier.
Claims (3)
1. one kind is adopted high-temperature oxidation method to prepare tin ash SnO
2The method of laminated film is characterized in that at fluorine-doped tin dioxide SnO
2: on the F film basis, fluorine-doped tin dioxide SnO
2: the F film resiativity is less than 1 * 10
-3Ω .cm, with high-temperature oxidation method by oxonium ion to fluorine-doped tin dioxide SnO
2: the F film diffusion, thus low-resistance high resistant composite membrane formed.
2. the method for claim 1, the work atmosphere in its high-temperature oxidation environment is that pure oxygen and/or pure oxygen carry hydrogen peroxide.
3. the method for claim 1, its high-temperature oxydation temperature is at 500 ℃ to 550 ℃.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100813802A CN1317740C (en) | 2004-12-01 | 2004-12-01 | Preparation of SnOz transient layer by high-temperature oxide method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100813802A CN1317740C (en) | 2004-12-01 | 2004-12-01 | Preparation of SnOz transient layer by high-temperature oxide method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1614744A CN1614744A (en) | 2005-05-11 |
| CN1317740C true CN1317740C (en) | 2007-05-23 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100813802A Expired - Fee Related CN1317740C (en) | 2004-12-01 | 2004-12-01 | Preparation of SnOz transient layer by high-temperature oxide method |
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101615638B (en) * | 2008-10-06 | 2012-12-05 | 四川大学 | CdTe thin-film solar cell with Te cushion layer |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4293594A (en) * | 1980-08-22 | 1981-10-06 | Westinghouse Electric Corp. | Method for forming conductive, transparent coating on a substrate |
| JPS5764986A (en) * | 1980-10-08 | 1982-04-20 | Ricoh Co Ltd | Manufacture of thin film photodiode |
| CN85102350A (en) * | 1984-12-28 | 1986-07-09 | M&T化学股份有限公司 | Make the liquid coating composition of high quality, high-performance, fluorine-containing doped tin oxide coatings |
| JPH05294673A (en) * | 1992-04-17 | 1993-11-09 | Asahi Glass Co Ltd | Production of glass coated with transparent electrically conductive film |
| CN1174487A (en) * | 1996-08-21 | 1998-02-25 | 无锡市现代技术发展公司 | Production process of transparent electrothermic film element |
| CN1196760A (en) * | 1996-05-06 | 1998-10-21 | 利比-欧文斯-福特公司 | Method for forming tin oxide coating on glass |
| US6235343B1 (en) * | 1998-06-19 | 2001-05-22 | Saint-Gobain Vitrage | Process for depositing a metal-oxide-based layer on a glass substrate and glass substrate thus coated |
-
2004
- 2004-12-01 CN CNB2004100813802A patent/CN1317740C/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4293594A (en) * | 1980-08-22 | 1981-10-06 | Westinghouse Electric Corp. | Method for forming conductive, transparent coating on a substrate |
| JPS5764986A (en) * | 1980-10-08 | 1982-04-20 | Ricoh Co Ltd | Manufacture of thin film photodiode |
| CN85102350A (en) * | 1984-12-28 | 1986-07-09 | M&T化学股份有限公司 | Make the liquid coating composition of high quality, high-performance, fluorine-containing doped tin oxide coatings |
| JPH05294673A (en) * | 1992-04-17 | 1993-11-09 | Asahi Glass Co Ltd | Production of glass coated with transparent electrically conductive film |
| CN1196760A (en) * | 1996-05-06 | 1998-10-21 | 利比-欧文斯-福特公司 | Method for forming tin oxide coating on glass |
| CN1174487A (en) * | 1996-08-21 | 1998-02-25 | 无锡市现代技术发展公司 | Production process of transparent electrothermic film element |
| US6235343B1 (en) * | 1998-06-19 | 2001-05-22 | Saint-Gobain Vitrage | Process for depositing a metal-oxide-based layer on a glass substrate and glass substrate thus coated |
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| Publication number | Publication date |
|---|---|
| CN1614744A (en) | 2005-05-11 |
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