CN107425088A - A kind of new heterojunction solar battery - Google Patents

A kind of new heterojunction solar battery Download PDF

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Publication number
CN107425088A
CN107425088A CN201710857818.9A CN201710857818A CN107425088A CN 107425088 A CN107425088 A CN 107425088A CN 201710857818 A CN201710857818 A CN 201710857818A CN 107425088 A CN107425088 A CN 107425088A
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China
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layers
solar battery
heterojunction solar
layer
solar cell
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CN201710857818.9A
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Inventor
杨恢东
张翠媛
宋香荣
夏锦辉
王菁
陈玉玲
彭炳荣
李俊魁
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Jinan university shaoguan institute
Jinan University
University of Jinan
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Jinan university shaoguan institute
Jinan University
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Priority to CN201710857818.9A priority Critical patent/CN107425088A/en
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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
    • H01L31/04Semiconductor 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 adapted as photovoltaic [PV] conversion devices
    • H01L31/06Semiconductor 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 adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier
    • H01L31/075Semiconductor 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 adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PIN type
    • H01L31/077Semiconductor 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 adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PIN type the devices comprising monocrystalline or polycrystalline materials
    • 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
    • H01L31/0248Semiconductor 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 characterised by their semiconductor bodies
    • H01L31/0256Semiconductor 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 characterised by their semiconductor bodies characterised by the material
    • H01L31/0264Inorganic materials
    • H01L31/0328Inorganic materials including, apart from doping materials or other impurities, semiconductor materials provided for in two or more of groups H01L31/0272 - H01L31/032
    • H01L31/0336Inorganic materials including, apart from doping materials or other impurities, semiconductor materials provided for in two or more of groups H01L31/0272 - H01L31/032 in different semiconductor regions, e.g. Cu2X/CdX hetero-junctions, X being an element of Group VI of the Periodic System
    • 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
    • Y02E10/547Monocrystalline silicon PV cells

Abstract

The invention discloses a kind of new heterojunction solar battery, including dorsum electrode layer, the P layers on dorsum electrode layer, the Window layer on P layers, the Window layer is to be doped with Al ZnO film;The ZnO film and P layers for being doped with Al form PN junction.Oxidic, transparent, conductive layers and N-type Window layer are combined into one by the present invention, are formed NIP type heterojunction solar batteries, by the way that hetero-junctions is prepared with the material of different band gap on the monosilicon, is improved the efficiency of solar cell, add the utilization rate of solar energy.

Description

A kind of new heterojunction solar battery
Technical field
The present invention relates to the research field of solar cell, specifically hetero-junction thin-film solar cell.
Background technology
Solar cell is also known as photovoltaic cell, is a kind of semiconductor devices for solar energy directly being converted electric energy, and its work is former Reason is:When semiconductor wafer is by illumination, if photon energy is more than the energy gap of semiconductor, valence-band electrons can absorbs The energy of photon, conduction band is leapt to by forbidden band, due to the effect of built in field, occur one at the both ends of PN junction and produced because of illumination Raw electromotive force, material is thus formed power supply, you can is powered to external circuit.
Since preparing first solar cell from the AT&T Labs in the U.S. in 1954, it is swift and violent that solar cell has started its The step of development, distinguished from the maturity of solar cell generation technology, solar cell can be divided into following several stages:The first generation Crystal-silicon solar cell, the various thin film solar cells of the second generation, the third generation solar cell:Various super stacked solar cell, cascade solar cells, heat Photovoltaic cell (TPV), SQW and quantum dot superlattice solar cell, Intermediate Gray solar cell, it is upper conversion solar cell, lower turn Change the new ideas solar cells such as solar cell, hot carrier solar cell, impact ionization solar cell.
At this stage using the thin-film type solar cell of photoelectric effect work as main flow, and the implementation to be worked with photochemical effect Solar cell is then also in the budding stage.The typical structure of thin film solar cell is as shown in Figure 1 and Figure 2.Use different materials With technology of preparing, solar battery structure can be different, but basic solar battery structure can be divided into:Dorsum electrode layer, P layers, N layers (Window layer), oxidic, transparent, conductive layers and five major parts of finger-type Top electrode, the solar cell of NIP types also include I layers.
The effect of dorsum electrode layer (or bottom electrode or hearth electrode) is to will be moved to electronics or the hole taking-up of lower surface, with Form foreign current and be supplied to external loading.
P layers and the contact of N layers form PN junction, and under thermal equilibrium state, internal electric field is formed between P layers and N layers.Tied for NIP Structure, photo-generated carrier are mainly formed at intrinsic layer, and in the presence of internal electric field, light induced electron flows to N layers, and photohole flows to P layers.Under open-circuit condition, light induced electron tires out in N laminations, and photohole tires out in P laminations.At this moment photogenerated charge is in P layers and N layers Electric field is produced, the photohole in the light induced electron and P layers that make to accumulate in N layers has the trend spread in the opposite direction, with Offset the collected current of photo-generated carrier.When reaching dynamic equilibrium between the collected current under dissufion current and built-in field action When, then will there is no electrostatic current in intrinsic layer.
The effect of oxidic, transparent, conductive layers is to reduce incident visible ray to reflect on the surface of device.
The effect of finger-type Top electrode is to will move to electronics or the hole taking-up on surface, and outside is supplied to form foreign current Load.In upper surface, the electrode of plane of illumination is made up of several main grids in finger-type more.
The development of crystal-silicon solar cell is limited due to preparing the factors such as cost is high, floor space is big, compared to crystal silicon Solar cell, it is exactly that cost is low, preparation technology is simple the characteristics of silicon-based thin film solar cell maximum.Thin film solar cell can sink Product is on glass, stainless steel, plastics, ceramic substrate or film, and the semiconductor layer of thin film solar cell is very thin (several microns or several Ten microns of thickness), can the active layer of filming must strengthen its mechanical performance with substrate, the semiconductive thin film formed on substrate It can be polycrystalline or amorphous, not necessarily use monocrystal material.Therefore, the film of different materials is researched and developed too Positive electricity pond is the effective way for reducing cost, to greatly save solar cell material, reduces production cost.
PN junction is made with homojunction in most domestic silica-based solar cell at present, less efficient.Heterojunction solar battery exists A hetru P-N junction is formed on the interface that two kinds of semi-conducting materials of different energy gaps are in contact.Hetero-junctions has following excellent Point:(1) heterojunction solar battery is formed by the different material of energy gap, can broadening to the absorption spectra of sunshine, favorably Absorbed in broad band, so as to improve efficiency;(2) increase built in field, improve injection efficiency, compared with homojunction, hetero-junctions tool There is bigger built in field, make non-equilibrium few electron current increase of injection knot both sides, so as to increase open-circuit voltage and short circuit current; (3) reduce raw silicon consumption, reduce cost, the development of hetero-junctions makes thin film technique arise at the historic moment, so as to which battery is grown Glass, ceramics in low cost is even in flexible substrate.
The content of the invention
To solve the technical problem present in prior art, the present invention provides a kind of by oxidic, transparent, conductive layers and N-type window The NIP type heterojunction solar batteries that mouth layer is combined into one, are prepared heterogeneous by the monosilicon with the material of different band gap Knot, the efficiency of solar cell is improved, add the utilization rate of solar energy.
The present invention is realized using following technical scheme:A kind of new heterojunction solar battery, including dorsum electrode layer, position P layers on dorsum electrode layer, the Window layer on P layers, the Window layer are to be doped with Al ZnO film;It is doped with Al ZnO film forms PN junction with P layers.
Preferably, the thickness range of the ZnO film for being doped with Al is:20nm~600nm.
Preferably, the Al doping ratios scope is:0.5%~8%.
Preferably, the P layers are P-Si substrates.The heterojunction solar battery also includes I layers;The I layers are to be arranged on Layer of semiconductor material between P-Si substrates and ZnO film, the lattice constant and energy gap of the semi-conducting material are situated between In P-Si substrates, ZnO film lattice constant and energy gap between.
Silica-based solar cell phase of the N-ZnO/i layers/P-Si heterojunction solar batteries of the present invention with PN junction is made of homojunction Than having the following advantages that:
1st, oxidic, transparent, conductive layers and N-type Window layer are combined into one to form NIP type hetero-junctions, can not only make preparation work Skill is simple, can also reduce the making of transparency conducting layer so as to reduce cost.
2nd, hetero-junctions is formed by the different material of energy gap, can broadening to the absorption spectra of sunshine, be advantageous to wide range Band absorbs, so as to improve the efficiency of solar cell.
3rd, compared with homojunction, hetero-junctions has bigger built in field, makes non-equilibrium few electron current of injection knot both sides Increase, so as to increase open-circuit voltage and short circuit current.
4th, raw silicon consumption can be reduced, reduce cost, the development of hetero-junctions makes thin film technique arise at the historic moment, so as to Battery is grown on the glass, ceramics or even flexible substrate of low cost.N-ZnO/i layers/P-Si hetero-junctions sun of the present invention Battery had with the characteristics of material is few, energy consumption is low, cost is low and technique is simple.
Brief description of the drawings
Fig. 1 is existing PN types solar cell junction composition;
Fig. 2 is existing NIP types solar cell junction composition;
Fig. 3 is solar battery structure figure of the present invention.
Embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited In this.
Embodiment
The window layer material of solar cell does not require nothing more than that band gap is wide, also requires there is higher conductance, to provide high built-in electricity Field and good charge collection channel, reduce series resistance.Transparent conductive oxide (TCO) film falls within optical material, and it has There is higher electrical conductivity, energy gap is big, there is higher transmissivity in visible region, and near, middle infrared has high reflectivity, With ultraviolet cut-on characteristic, there is stronger Decay Rate to microwave and there is characteristic of semiconductor.
ZnO is a kind of II-VI group semiconductor material with wide forbidden band, is at ambient pressure hexagonal wurtzite structure, belongs to hexagonal crystal system. At room temperature, its energy gap is 3.3eV.Because ZnO optical energy gap is wanted in more than 3.1eV, the energy than visible ray Greatly, so there is very high transmitance in visible-range, its transmitance is more than 85%.
Undoped ZnO film is because intrinsic defect shows weaker N-type characteristic, after adulterating Al, its electric conductivity Can it be significantly improved with N-type characteristic.After in appropriate A1 elements incorporation ZnO film, the crystal structure of ZnO film is simultaneously Do not change.The A1 elements of incorporation instead of the position of part Zn atoms, because A1 atom outermost layers have three electronics, Zn Atom outermost layer has two electronics, A13+Substitute Zn2+Afterwards, two valence electrons in A1 atoms combine with O atom, remaining One valence electron separates from foreign atom, and this valence electron is readily available energy, and transitting to conduction band from donor level turns into Free electron, it is conductive so as to be participated in the presence of external electric field.Therefore appropriate incorporation A1 atoms can increase the content of net electronics, So as to improve the electrical conductivity of film.
Al3+Doping do not change ZnO crystal structure, but Al3+It instead of part Zn in crystal structure2+Position Put.On the one hand, Al doping can influence surface topography, carrier number of film etc., and then influence the photo electric of AZO films Energy;On the other hand, if Al doping concentrations are excessive, film can strengthen the scattering power of electronics and light, so as to cause the light of film Electrical property reduces.Therefore, the Al doping ratio scopes that are taken of the present invention are:0.5%~8%, the thickness model of AZO films after doping Enclose for:20nm~600nm.
After being deposited on the Al doping ZnO on P-Si substrates, AZO films are formed, AZO films can form PN junction with P-Si. Because the energy gap of AZO films is larger, it is seen that the lower energy photon of light part can pass through AZO film layers and by the sky of P-Si sides Between charged region collect, and AZO film contacts layers have the characteristic of metalloid, can improve the photoresponse of hetero-junctions.Therefore deposit AZO films on P-Si substrates can both be used as light window layer, can also be used as semiconductor layer.
Presence due to surface state and boundary caused by lattice mismatch, thermal expansion coefficient difference between AZO films and Si substrates The factors such as planar defect change the architectural characteristic of space-charge region so that it is special that AZO/P-Si hetero-junctions shows nonideal electricity Property.
If increasing by a layer lattice constant between P-Si and ZnO and semiconductor material that energy gap all falls between Expect (I layers), i.e. the lattice constant of semi-conducting material is between P-Si lattice constant and ZnO lattice constant, energy gap Also between P-Si energy gap and ZnO energy gap.On the one hand can using more band structures of this bandwidth gradual change To improve the utilization rate of sunshine;Moreover it is possible to realize, the raising sun identical in the direction of spectral response caused by regional The conversion efficiency of energy battery.On the other hand both lattice mismatches can be alleviated, improves the crystal mass of ZnO film, improved and carry The mobility of son is flowed, and suppresses the decay of hetero-junctions.
The increased semi-conducting material I layers of institute can be cushion or absorbed layer.If I layers are as absorbed layer, one of special Sign is exactly to have the higher absorption coefficient of light, and main light is absorbed in I layers, and the photo-generated carrier in this layer can be received effectively Collection.Can there are cadmium telluride, GaAs, cadmium sulfide etc. as the material for preparing of absorbed layer.In addition, in order to reduce the shadow of interfacial state Ring, one layer of cushion can be added between the interface of two kinds of materials by the technique of various passivation, i.e. I layers as cushion, To reduce the dangling bonds on heterojunction boundary, so as to reduce interface state density.
I layers are inserted in AZO/P-Si hetero-junctions can not only reduce interface state density, reduce answering for solar cell interface Electric current is closed, so as to greatly improve the open-circuit voltage of solar cell, the transport and collection of photo-generated carrier can also be strengthened, reduce it Recombination rate, so as to improve the performance of heterojunction solar battery.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification, Equivalent substitute mode is should be, is included within protection scope of the present invention.

Claims (7)

1. a kind of new heterojunction solar battery, including dorsum electrode layer, the P layers on dorsum electrode layer, on P layers Window layer, it is characterised in that the Window layer is to be doped with Al ZnO film;The ZnO film and P layers for being doped with Al are formed PN junction.
2. heterojunction solar battery according to claim 1, it is characterised in that the thickness of the ZnO film for being doped with Al Spending scope is:20nm~600nm.
3. heterojunction solar battery according to claim 1 or 2, it is characterised in that the Al doping ratios scope is: 0.5%~8%.
4. heterojunction solar battery according to claim 1, it is characterised in that the P layers are P-Si substrates.
5. heterojunction solar battery according to claim 4, it is characterised in that the heterojunction solar battery also includes I Layer;The I layers are the layer of semiconductor material being arranged between P-Si substrates and ZnO film, the lattice of the semi-conducting material Constant and energy gap between P-Si substrates, ZnO film lattice constant and energy gap between.
6. heterojunction solar battery according to claim 5, it is characterised in that the I layers are cushion or absorbed layer.
7. heterojunction solar battery according to claim 5, it is characterised in that the I layers prepare material for cadmium telluride, GaAs or cadmium sulfide.
CN201710857818.9A 2017-09-21 2017-09-21 A kind of new heterojunction solar battery Pending CN107425088A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109742093A (en) * 2018-12-18 2019-05-10 暨南大学 A kind of enhancing blu-ray type silicon substrate avalanche photodiode array and preparation method thereof

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CN103956391A (en) * 2014-04-11 2014-07-30 中国科学院宁波材料技术与工程研究所 AZO/Si heterojunction solar battery and manufacturing method thereof

Patent Citations (2)

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Publication number Priority date Publication date Assignee Title
CN102214708A (en) * 2010-04-08 2011-10-12 通用电气公司 Thin film solar cell and manufacturing method thereof
CN103956391A (en) * 2014-04-11 2014-07-30 中国科学院宁波材料技术与工程研究所 AZO/Si heterojunction solar battery and manufacturing method thereof

Non-Patent Citations (2)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109742093A (en) * 2018-12-18 2019-05-10 暨南大学 A kind of enhancing blu-ray type silicon substrate avalanche photodiode array and preparation method thereof

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