CN105140338B - A kind of inexpensive FeS2The preparation method of thin film solar cell - Google Patents

A kind of inexpensive FeS2The preparation method of thin film solar cell Download PDF

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CN105140338B
CN105140338B CN201510450904.9A CN201510450904A CN105140338B CN 105140338 B CN105140338 B CN 105140338B CN 201510450904 A CN201510450904 A CN 201510450904A CN 105140338 B CN105140338 B CN 105140338B
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fes
film
zno
solar cell
thickness
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CN105140338A (en
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杨雯
段良飞
杨培志
李学铭
赵恒利
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Yunnan Normal University
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1828Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIBVI compounds, e.g. CdS, ZnS, CdTe
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • Y02E10/543Solar cells from Group II-VI materials
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

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  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Electromagnetism (AREA)
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  • Photovoltaic Devices (AREA)

Abstract

Patent of the present invention provides a kind of inexpensive FeS2The preparation method of thin film solar cell.Mainly by preparing molybdenum back electrode on substrate, FeS is prepared on back electrode2Film simultaneously carries out vulcanization and forms P layers, and then prepares CdS film as cushion, and i ZnO and ZnO are prepared on the buffer layer:Al films, finally prepare MgF2Antireflective film, by preparing Ag Mg alloys after laser ablation and cleaning as preceding electrode, so as to prepare structure for substrate/Mo/FeS2/CdS/i‑ZnO/ZnO:Al/MgF2The FeS of/Ag Mg2Thin film solar cell.Its core material FeS in the solar cell of this structure2It is big, nontoxic with ZnO component reserves, can effectively reduce the cost of solar cell, FeS2Belong to the binary compound of yellow cubic structure, have the advantages that absorption coefficient is big, band gap is adjustable and good stability, is one of preferable photovoltaic material, be expected to be stablized, efficient solar cell.

Description

A kind of inexpensive FeS2The preparation method of thin film solar cell
Technical field
The present invention relates to a kind of inexpensive FeS2The preparation method of thin film solar cell, belongs to efficient, inexpensive, environment friendly Good photovoltaic cell technical field.
Background technology
Efficiently, the research of the critical material and device of low cost and environmentally friendly new solar cell is large-scale application Solar cell, solves the key of fossil energy increasingly depleted and environmental problem, is also the focus and difficulty of solar cell area research Point.
It is only way of the following scale using solar power generation to explore inexpensive thin film solar cell material.Curing It is ferrous(FeS2)The binary compound of nontoxic, reserves very abundant as component, with suitable energy gap, higher The advantages of absorption coefficient of light and enough carrier diffusion lengths.Therefore, FeS2It is a kind of ideal low cost environment friend Good type thin film solar cell material.One of key of its final application is the synthetic method for developing low cost, is prepared in air The pure Emission in Cubic FeS of middle stabilization2Material.FeS2It is latent with good application in terms of the electrooptical devices such as manufacture solar cell Power, also can be used as the low-gap semiconductor sensitized material of dye-sensitized solar cells.The theoretical research of early stage(A.Ennaoui, S.Fieehter,C. H. Pettenkofer, N.Alonso-Vante, K.Buker, M.Bronold, C.Hopfeer, H.Tributseh, Irondisulfideforsolarenergyeonversion, SolarEnergyMaterialsandSolarCells,1993,29(4): 289-370)Think to utilize FeS2Pn-junction can be made And the solar cell of pin structures, and then realize opto-electronic conversion.The formation of pn-junction structure therein can be controlled by doped chemical System.According to P. P. Altermatt et al.(P. P. Altermatt, T. Kiesewetter, K. Ellmer, H. Tributseh, Speeifying targets of futurer esearch in Photovoltaie devices eontaining Pyrite (FeS2) by numerical modeling, Solar Energy Materials and Solar Cells, 2002,71(2):181-195)On FeS2The calculation simulation analysis of monocrystalline and film, the pn-junction structure sun The photoelectricity transfer efficient of battery is up to 18.5%.
In recent years, people are to FeS2The other application of semi-conducting material has been also carried out research, such as U.S. patent Nos: Method to synthesize colloidal iron pyrite(FeS2) nanocrystals and fabric ate iron pyrite thin film solar cells(US20110240108A1):The public one kind that provides of patent is used for efficiently, The p-n heterojunction pyrite of low cost(FeS2)The manufacture system and method for solar cell.Including pyrite(FeS2)Thin battery Component includes Window layer, absorbed layer and electrode.The method that synthesis colloid pyrite nanocrystal is provided.Additionally provide a kind of chemistry Legal system makes high efficiency, the method for the solar cell of the pn hetero-junctions pyrite of low cost.U.S. patent Nos:Counter electrode and dys-sensitized solar cell using the same(US20140158186A1), patent Disclose a kind of back electrode and DSSC.DSSC includes:Preceding electrode, back electrode and electricity Electrolyte solution, back electrode includes conductive layer and catalyst layer.The FeS that catalyst layer includes2, by electrolyte be arranged in preceding electrode and To between electrode.Therefore it is by FeS2Modification ITO is applied in dye-sensitized solar cells, and the present invention can be substantially reduced back of the body electricity Pole and the manufacturing cost of DSSC.This patent is in back electrode molybdenum(Mo)Evaporated on layer and prepare FeS2Film conduct P-type layer, material band gap is 0.95eV ~ 1.37eV, different S contents and the band gap of microfabricated tunable control material;Again in P-type layer I-ZnO is prepared as N-type layer, material band gap is 3.2eV;In order that the band-gap between P-type layer and N-type layer is good, two Interlayer adds one layer of CdS(Eg=2.4eV)As cushion, ZnO is prepared on i-ZnO:Al as oxidic, transparent, conductive layers, most After prepare MgF2As antireflective film and preceding Electrode Ag-Mg alloys, so as to prepare FeS2Solar cell, comparatively speaking, this patent Have the advantages that process is simple, uniformity of film are good, easy to control.
The content of the invention
For the problem that background technology is proposed, patent of the present invention proposes a kind of inexpensive FeS2The preparation of thin film solar cell Method:One layer of Mo is first prepared on substrate as back electrode, FeS is prepared on back electrode2Film is simultaneously vulcanized as p-type Layer, in FeS2One layer of CdS film of upper preparation is used as cushion;I-ZnO and ZnO is prepared again:Al is used as N layers and transparent conductive oxide Layer, finally prepares MgF2Antireflective film, electrode before Ag-Mg alloys.Final structure of preparing is for Glass/Mo/FeS2/CdS/i-ZnO/ ZnO:Al/MgF2The FeS of/Ag-Mg2Thin film solar cell.
To realize above-mentioned target, the present invention uses following technological means.It is specific as follows:
A:The cleaning of substrate:It is substrate to use glass, is cleaned by ultrasonic using acetone, absolute ethyl alcohol and deionized water successively 10min~15min;
B:The preparation of back electrode:Using magnetically controlled DC sputtering coating system, the purity is used to be for 99.999% metal Mo targets Target, base vacuum is 6.0 × 10-4Pa, sputtering pressure is 1.0Pa, and sputtering power is 70W ~ 80W, is sputtered on a glass substrate It is back electrode to prepare Mo films, and thickness is 200nm ~ 300nm;
C:FeS2The preparation of film:Using electron beam vacuum evaporation coating membranous system, the FeS using purity more than 99.99%2 Grain is evaporation raw material, and base vacuum is 6.0 × 10-4Pa, evaporation pressure is 4.0 × 10-3Pa, line is 5mA ~ 15mA, in back of the body electricity It is extremely upper to prepare FeS2Film, thickness is 1.5um ~ 2.0um, the FeS prepared to evaporation2Film carries out vulcanizing treatment, FeS2Film is P-type;
D:The preparation of cushion:It is cushion to use CdS, using chemical bath(CBD)Method is in FeS2CdS is prepared on film Cushion, temperature is 65 DEG C ~ 75 DEG C, and thickness is 50nm ~ 60nm;
E:The preparation of Window layer:Using rf magnetron sputtering, sputtering prepares ZnO film for Window layer on buffer layer thin film, Base vacuum is 6.0 × 10-4Pa, sputtering pressure is 0.08Pa, and sputtering power is 100W ~ 120W, and thickness is 300nm ~ 350nm, Al films are prepared in the sputtering of ZnO film surface again, base vacuum is 6.0 × 10-4Pa, sputtering pressure is 1.0Pa, and sputtering power is 70W ~ 80W, thickness is 10 ~ 20nm and is made annealing treatment that annealing atmosphere is N2, annealing temperature is 300 DEG C, and annealing time is 30min ~ 40min, it is the ZnO of 250nm ~ 300nm to form thickness on ZnO top layers:Al is used as transparent conductive film;
F:The preparation of antireflective film:MgF is prepared using electron beam vacuum evaporation coating membranous system2Film is antireflective film, and background is true Sky is 4.0 × 10-4Pa, evaporation pressure is 4.0 × 10-3Pa, line is 5mA ~ 15mA, and 100nm MgF are prepared in Window layer2Subtract Anti- film;
G:Preceding electrode:It is electrode using the film surface evaporation Ag films being evaporated in vacuo after etching, base vacuum is 6.0 ×10-6Pa, sputtering pressure is 1.0Pa, and sputtering power is 70W ~ 80W, and thickness is 100nm.
The present invention has the advantage that and good effect compared with known technology:
1、FeS2Be it is a kind of have absorption coefficient big, component is simple, nontoxic and rich reserves, for preparing sun electricity Material usage, reduces cost can be reduced during pond;
2nd, this patent prepares FeS using positive sky evaporation coating system2Film, with film forming is uniform, rate of film build fast, crystallization Performance is good, it is easy to control the advantages of.
Brief description of the drawings:
A kind of inexpensive FeS that Fig. 1 is provided for the present invention2The preparation flow figure of thin film solar cell;
A kind of inexpensive FeS that Fig. 2 is provided for the present invention2The structure chart of thin film solar cell.
Specific embodiment:
Embodiment 1:
The present embodiment is according to the following steps:
1st, ultrasonic cleaning 10min, N are carried out to glass substrate respectively using acetone, absolute ethyl alcohol and deionized water successively2Blow It is dry;
2nd, using magnetron sputtering coating system, the molybdenum target with purity more than 99.999% is prepared on a glass substrate as target Back electrode, sputter gas are the Ar gas of purity 99.99%;Base vacuum is 6.0 × 10-4Pa, is passed through Ar gas, flow be 30sccm ~ 40sccm, regulation sputtering pressure is 1.0Pa, and power is 74w, and sputtering time is 60s ~ 100s, is sputtered on substrate and prepares 200nm The Mo films of ~ 300nm;
3rd, it is the FeS of 1.5um ~ 2.0um to use electron beam evaporation system to prepare thickness on back electrode surface2Film, background is true Sky is 4.0 × 10-4Pa, evaporation current is 0.65A ~ 0.75A, and voltage is set automatically with electric current, and high pressure is 80KV;Line 5mA ~ 15mA;The FeS that will be prepared2Membrane sample carries out vulcanization 25min ~ 30min in being put into tubular type vulcanizing oven, and Fe, S in regulation and control film contain Amount ratio;
4th, spend and prepare electrolyte from water(Cd of the electrolyte containing 1mol/L(CH3COO)2, the NH of 5mol/L2CSNH2, The CH of 1mol/L3COONH4, the NH of 0.4mol/L4OH), the pH value of solution is adjusted to 12 ~ 18, using three-electrode electro Chemical body Tie up to deposition oxygen CdS film layer in the electrolyte for preparing.Deposition process uses constant potential mode, under 70 DEG C of depositing temperature Carried out without stirring, deposition is controlled by monitoring deposited charge amount, sedimentation time about 30min ~ 60min, thickness be 5nm ~ 20nm;The CdS film sample of deposition is cleaned with deionized water, is dried naturally;
5th, using magnetron sputtering coating system, the ZnO target with purity more than 99.99% prepares ZnO thin as target on CdS Film, sputter gas are the Ar gas of purity 99.99%;Base vacuum is 6.0 × 10-4Pa, is passed through Ar gas, flow be 30sccm ~ 40sccm, regulation sputtering pressure is 0.68pa ~ 0.72pa, and power is 100W, and thickness is 300nm ~ 350nm;
6th, using magnetron sputtering coating system, the Al targets with purity more than 99.999% prepare back of the body Al as target on ZnO Film, sputter gas are the Ar gas of purity 99.99%;Base vacuum is 6.0 × 10-4Pa, is passed through Ar gas, flow be 30sccm ~ 40sccm, regulation sputtering pressure is 1.0pa ~ 1.2pa, and power is 74W, and thickness is 20nm ~ 30nm;
7th, the film sample of preparation is put into RTP photo-thermal quick anneal ovens, in N2Carried out with 300 DEG C ~ 350 DEG C under atmosphere Short annealing 25min so that i-ZnO thickness is 50nm, ZnO:Al thickness is in 250nm ~ 300nm;
8th, using electron beam vacuum evaporation coating membranous system, the MgF that thickness is 80nm ~ 100nm is prepared2Antireflective film, background is true Sky is 4.0 × 10-4Pa, evaporation current is 0.65A ~ 0.75A, and voltage is set automatically with electric current, and high pressure is 80KV;Line 5mA ~ 15mA;
9th, using electron beam vacuum evaporation coating membranous system, it is 120nm ~ 150nm's that thickness is prepared on film after etching Used as electrode, material selection purity is 99.999% Ag and Mg particles to Ag-Mg alloy firms, and base vacuum is 4.0 × 10-4Pa, Evaporation current is 0.65A ~ 0.75A, and voltage is set automatically with electric current, and high pressure is 80KV;Line 5mA ~ 15mA.
Embodiment 2:
The present embodiment is according to the following steps:
Similar to Example 1, during difference is battery structure, Selection utilization ZnS is cushion.
Embodiment 3:
The present embodiment is according to the following steps:
It is similar to Example 1, during difference is battery structure, do not use cushion.
Embodiment 4:
The present embodiment is according to the following steps:
Similar to Example 1, during difference is battery structure, Selection utilization FTO is back electrode.

Claims (1)

1. a kind of inexpensive FeS2The preparation method of thin film solar cell, it is characterized in that:A layer thickness is prepared on substrate is The metal molybdenum of 200nm-300nm(Mo)Used as back electrode, it is 1.5um-2.0um's to use evaporation to prepare thickness on Mo films to film FeS2Film simultaneously carries out P layers of vulcanizing treatment formation, in FeS2It is the CdS film of 5nm-20nm that electrochemical deposition thickness is used on film Used as cushion, it is 300nm ~ 350nm to be sputtered in CdS film and prepare i-ZnO thickness, and thickness is prepared in the sputtering of i-ZnO surfaces It is the Al films of 25nm-30nm, and combines fast -Hankel transform treatment, one layer of ZnO of 20nm-50nm is formed on surface:Al films Used as oxidic, transparent, conductive layers, finally evaporation prepares the MgF that thickness is 80nm-100nm2Antireflective film, by laser ablation and clearly Use sputtering to be prepared for Ag-Mg alloy of the thickness for 120nm-150nm as preceding electrode after washing, be lining so as to prepare structure Bottom/Mo/FeS2/CdS/i-ZnO/ZnO:The FeS of Al/MgF2/Ag-Mg2Thin film solar cell;
Wherein, it is the FeS of 1.5um-2.0um to use electron beam evaporation system to prepare thickness on back electrode surface2Film, base vacuum It is 4.0 × 10-4Pa, evaporation current is 0.65A-0.75A, and voltage is set automatically with electric current, and high pressure is 80KV, line 5mA- 15mA;The FeS that will be prepared2Membrane sample carries out vulcanization 25min-30min in being put into tubular type vulcanizing oven.
CN201510450904.9A 2015-07-29 2015-07-29 A kind of inexpensive FeS2The preparation method of thin film solar cell Expired - Fee Related CN105140338B (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1253665A (en) * 1998-04-29 2000-05-17 纳恩吉奥·拉·维克伽 Semiconductor element, especially solar cell and method for production thereof
CN101768728A (en) * 2010-01-15 2010-07-07 深圳大学 Method for preparing doped ZnO-based film through magnetron sputtering

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8344243B2 (en) * 2008-11-20 2013-01-01 Stion Corporation Method and structure for thin film photovoltaic cell using similar material junction

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1253665A (en) * 1998-04-29 2000-05-17 纳恩吉奥·拉·维克伽 Semiconductor element, especially solar cell and method for production thereof
CN101768728A (en) * 2010-01-15 2010-07-07 深圳大学 Method for preparing doped ZnO-based film through magnetron sputtering

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Comparison of pyrite thin films obtained from Fe and natural pyrite powder";C.D las Heras 等;《APPLIED SURFACE SCIENCE》;19910602;第50卷;第505页左栏第1-2段 *

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