CN102244115A - Solar cell with inorganic film absorbing layer - Google Patents
Solar cell with inorganic film absorbing layer Download PDFInfo
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- CN102244115A CN102244115A CN2010101677872A CN201010167787A CN102244115A CN 102244115 A CN102244115 A CN 102244115A CN 2010101677872 A CN2010101677872 A CN 2010101677872A CN 201010167787 A CN201010167787 A CN 201010167787A CN 102244115 A CN102244115 A CN 102244115A
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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
- 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
- Y02E10/542—Dye sensitized solar cells
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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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Abstract
The invention relates to the solar cell field, more particularly to a solar cell with an inorganic film absorbing layer. The solar cell comprises an n type semiconductor porous layer, an ETA layer and a p type semiconductor layer. The n type semiconductor porous layer has a monocrystalline structure and a ZnO nano-rod array film that is vertical and well-organized is employed. Diameters of the ZnO nanorods are 50 to 100 nanometers; space between the each two nanorods is 80 to 150 nanometers and a length of each nanorod is 100 nanometers to 10 micros. The ETA layer employs CuInS2 or CuInSe2 as materials and a thickness of the layer is between 15 and 25 nanometers and the thickness is even. The p type semiconductor layer is filled by CuSCN with densification. The solar cell provided in the invention is a novel cell that is developed on the basis of a dye-sensitized solar cell (DSC). The solar cell provided in the invention has the same advantages as the DSC, wherein the advantages include short path of charge transmission, low cost of raw materials, and simple equipment and manufacturing process; besides, the solar cell also has the same advantages as a traditional cell, wherein the advantages include sturdy and durable performance and convenience for modularization preparation; therefore, the solar cell provided in the invention provides a new way for development of the solar cell.
Description
Technical field
The present invention relates to area of solar cell, be specifically related to a kind of inorganic thin film absorbed layer solar cell.
Background technology
Current two ultimate challenges that face in countries in the world are energy shortage and amblent air temperature problem, and all relevant with traditional energy resource consumption mode, the fossil energy of promptly burning (comprising oil, coal and natural gas etc.).It is never exhausted that solar cell has resource (sun), CO
2Deng the optimal vigor of gas zero discharge, be the basic outlet that solves these two problems, but too high battery manufacturing cost has restricted its large-scale promotion application.Academia and industrial circle generally believe that the development of solar cell is by first generation monocrystaline silicon solar cell, solar cells such as second generation polysilicon, amorphous silicon, developing into the third generation solar cell of today, is exactly Copper Indium Gallium Selenide CIGS compound film solar cells such as (mixing Ga among the CIS).With regard to its cost of electricity-generating, the equipment cost of electricity-generating of silion cell is 2.8-3.3 unit/kilowatt hour, and the cost of electricity-generating of CIGS hull cell is 1.5-2.1 unit/kilowatt hour, and the thermal power generation cost is 0.2 a yuan/kilowatt hour, and the cost of electricity-generating of conventional solar cells is still 7-16 times of traditional cost of electricity-generating.Therefore, be necessary to strengthen the research and development of novel solar battery, significantly reducing the battery cost, thereby promote the large-scale application and the industrialization process of solar cell.
Dye-sensitized solar cells (Dye-sensitized solar cell, DSC) be a kind of novel battery that development in recent years is got up, the structure of DSC is made up of mainly nano porous semiconductor film, dye sensitizing agent, redox electrolytes matter, several parts such as electrode and conductive substrates is formed.Nano porous semiconductor film is generally metal oxide (TiO2, SnO2, ZnO etc.), accumulates on the glass plate of nesa coating the negative pole as DSC.Electrode as reducing catalyst, is being had the platinum that plates on glass of nesa coating usually.Sensitizing dyestuff is adsorbed on the nano porous titanium dioxide face.What fill between both positive and negative polarity is the electrolyte that contains oxidation-reduction pair, and that the most frequently used is I3/I-.
The DSC operation principle is as follows:
(1) dye molecule is subjected to behind the solar light irradiation by ground state transition to excitation state;
(2) dye molecule that is in excitation state is injected into electronics in the semi-conductive conduction band;
(3) electrons spread is to conductive substrates, and the back flows in the external circuit;
(4) dyestuff that is in oxidation state is reduced the electrolyte reducing/regenerating of attitude;
(5) electrolyte of oxidation state is reduced after electrode is accepted electronics, thereby finishes a circulation.
But DSC battery obvious defects is:
(1), the light-absorption layer of DSC battery adopts is metal complex dye, the compound of rare metal such as ruthenium or rhenium etc. normally, following large-scale application is subjected to raw-material serious restriction.
2, high efficiency DSC battery can only adopt liquid electrolyte to realize, this brings difficulty to futurity industry production and prolonged application, must consider the encapsulation technology and the long-time stability of battery.Although existing researcher attempts to adopt solid electrolyte to replace liquid electrolyte, because of the matching problem of itself and organic dyestuff does not obtain obvious breakthrough always.
Summary of the invention
The object of the present invention is to provide a kind of inorganic thin film absorbed layer solar cell, it is to develop and the next new battery of a class on the basis of DSC battery, it has that the charge transfer path of dye-sensitized solar cells is short, the cost of raw material is low concurrently, equipment and the simple advantage of manufacture process, have sturdy and durable, the advantage that is easy to modularization preparation of conventional batteries concurrently, for the development of solar cell provides new way.
The present invention solves the technical scheme that its technical problem takes: this kind inorganic thin film absorbed layer solar cell, comprise n N-type semiconductor N porous layer, semiconductor light-absorption layer and p type semiconductor layer, wherein, n N-type semiconductor N porous layer is deposited on the conductive substrates, semiconductor absorption layer evenly coats the nano grain surface of n N-type semiconductor N porous membrane, the p type semiconductor layer is filled in the preceding two-layer space that stays, it is characterized in that, described n N-type semiconductor N porous layer is a mono-crystalline structures, adopt vertical orderly ZnO nano-stick array thin film, described ZnO nanometer rods diameter is the 50-100 nanometer, and interrod spacing should be the 80-150 nanometer, excellent length 100 nanometers-10 micron; Described semiconductor light-absorption layer CuInS
2Or CuInSe
2Between thickness 15-25 nanometer, thickness is even; Described p type semiconductor layer is filled for the CuSCN densification.
N N-type semiconductor N porous layer is deposited on the conductive substrates, be the n N-type semiconductor N be again the absorbed layer carrier, play a part to collect and transmission light induced electron and Window layer; Semiconductor absorption layer (ETA) works the photon generation charge carrier effect that absorbs; Before being filled into, p type semiconductor layer, densification in the two-layer space that stays, work to collect, transmit photohole and Window layer.The part of battery is the sandwich structure (n type layer/ETA layer/p type layer) of n-i-p type, and working mechanism is: semiconductor light-absorption layer (ETA) is in the internal electric field zone of the two formation between n type semiconductor layer and p type semiconductor layer.During illumination, most of photon can see through the n type semiconductor layer and arrive the semiconductor light-absorption layer, and semiconductor absorption layer absorbs photon and inspires electronics and hole.Under the internal electric field effect, electron transition is to n type semiconductor layer one side, and hole transition is to p type semiconductor layer one side, and electronics separates back formation photoelectric current with the hole, and that photovoltage is a conduction band between n type p type semiconductor layer and the semiconductor light-absorption layer (ETA) is poor.
The invention has the beneficial effects as follows:
Compare with hull cell with traditional silion cell, the advantage of battery of the present invention (ETA battery) is:
1, there are a large amount of interfaces in inside battery, and repeatedly scattering, reflected sunlight absorb thereby produce repeatedly sunlight, and the efficiency of light absorption height is even very thin light-absorption layer thickness (15-25 nanometer) just can satisfy the extinction requirement;
2, the semiconductor light-absorption layer of ETA battery has strengthened internal electric field E as thin as a wafer greatly
Bi, the separative efficiency height of photo-generated carrier; Electron diffusion path is short, has reduced the requirement to ETA material crystalline quality and defect concentration, allows to adopt low-cost preparation technology.
The ETA battery just is being based on the advantage on solid state and stability, the new battery of a class that comes from the development of DSC battery.The ETA battery has adopted inorganic compound semiconductor to make light-absorption layer, solve above-mentioned two problems (solid state and stability) well, and the charge transfer path that has dye-sensitized solar cells concurrently is short, the cost of raw material is low, sturdy and durable, the advantage that is easy to the modularization preparation of equipment and simple advantage of processing procedure and conventional batteries, for the development of solar cell provides new way.Show as:
(1) raw material aspect
2007, the output of domestic solar cell was about 1180MW, and 300MW compared with the same period of last year increases by 3 times, and the output of whole world solar cell only is about 4000MW, surpassed 1/4 of world wide production.Silion cell thickness is the 350-450 micron, consuming 13 tons of polysilicons by every production 1MW solar cell calculates, domestic manufacture of solar cells manufacturer consumes 15340 tons of polysilicons altogether, and the polysilicon production capacity of China has only 1000 tons, the production breach of polysilicon reaches 14340 tons, can only depend on import, the price that makes polysilicon increases to present 300 dollars/ton from initial 20 dollars/ton.This causes big characteristics of present China photovoltaic industry ' to put both ends of the production process ': 95% raw material need import, and 95% solar cell then is outlet.The CIGS hull cell is another kind of with the industrialization type, also is generally acknowledge most effective at present, the battery that stability is best, but its development is subjected to the restriction of phosphide element shortage.In the CIGS battery, cigs layer thickness is about the 2-3 micron, and the reserves of whole world indium are only enough produced 5000 square kilometres of battery sheets, all is used to produce the energy of being supplied and only accounts for about 6% of whole world energy-output ratio.Although its cost has only half of silion cell at present, component price 12-20 unit/W
pBut its long term growth will be subjected to raw-material restriction, and product cost also will rise with the increase of output.For the ETA battery, only need some chemical reagent commonly used in the preparation, avoid using rare metal, have abundant raw materials, lower-price characteristic.The battery operated layer of the ETA of this project exploitation gross thickness is about 4 microns, wherein light-absorption layer (CIS layer) thickness account for gross thickness less than 1/8, be equivalent to the CIGS hull cell consume the indium amount less than 1/8.The cell area that the indium reserves are made will be able to be enlarged 8 times, correspondingly the energy of its supply rises to 48% of world energy sources total flow.
The general commercialization efficient of silicon solar cell is at 10-13%, 27 yuan/watt of battery costs.The thickness of CIGS is about the 2-3 micron, and its cost has only half of silion cell, component price 12-20 unit/W
p, be best battery of current battery performance and life-span, but its long term growth will be subjected to raw-material restriction, product price also can rise gradually with the increase of output.The ETA battery cost also can by with the contrast of the dye-sensitized cell cheaply of generally acknowledging at present in obtain.The cost of dye cell is the 1/5-1/10 of silion cell at present, and its cost of electricity-generating is equivalent to 2 times of traditional generation mode basically.But used therein dyestuff is the organic coordination compound of rare metal ruthenium or rhenium, and the cost of this dyestuff is very high, is 10,000 yuan/gram, and is all more much higher than the price of gold, and is subjected to the restriction of resource.The ETA battery of this project exploitation only need change dyestuff wherein into CIS, changes wherein iodine electrolyte into CuSCN.Amounting to its cost and have only 1/2 of dye cell, is the 1/10-1/16 of silion cell.Therefore, the ETA battery is minimum in the present manufacture of solar cells cost, and also has the very big space to other battery types (quantum dot cell) expansion more cheaply.
(2) energy resource consumption aspect
Energy resource consumption is that manufacture of solar cells must be considered.As, power consumption accounts for more than 50% in the silion cell total production cost.The cost of home products is then at 70～80 dollars/kg at present.In the ETA battery production, the ratio that the preresearch estimates energy-output ratio occupies in total cost is approximately 15%.And in our production technology adopt the water-baths heating more, and if again the bath solution of upstream is used for downstream water-bath heating, being reused, energy resource consumption can further drop to about 7%.In addition, although the use of solar energy is pollution-free nothing discharging.But a unavoidable fact is to have many environment unfavorable factors in the raw-material production of solar energy.Such as silion cell; in the polysilicon production process, the cost of polysilicon raw material in entire cell occupies more than 60%, and can produce a kind of silicon tetrachloride accessory substance in the production process of polysilicon usually; harmfulness to environment is very big, has also run counter to the original intention of environmental protection.Production technology of this project and raw material all are environmentally friendly mostly, can not bring environmental hazard basically.
(3) overcome the thinking set that research experience brings.
Adopt the physical vapor and the chemical vapor deposition method of high-end devices can't satisfy light-absorption layer at ZnO or TiO
2The requirement of uniform deposition in the porous layer.Mainly be that these depositing operations are directed flow when deposition under the driving of deposition precursor body weight power or carrier gas thrust.The presoma directed flow also can produce shadow effect when running into porous layer, just as solar irradiation is mapped on the object can shading, nanometer rods dorsad a side of gas transmission be difficult on the deposition CIS layer or sedimentary deposit very thin.When battery operated, these parts very thin or that expose can produce electric leakage, and the part electric current that sunlight inspires will be consumed in the battery, can't form operating current.Experimental technology when the physics that contains high-end devices of report or chemical gaseous phase technology are silion cell and hull cell at present, the set that research experience brings causes people to pay close attention to these advanced technologies of preparing more, and has ignored the low-cost synthetic technology on the chemical industry.Advantage of the present invention exactly is to adopt chemical synthesis process, for the ETA battery industry production of high-efficiency and low-cost is laid a good foundation.
Embodiment
This kind inorganic thin film absorbed layer solar cell, comprise n N-type semiconductor N porous layer, semiconductor light-absorption layer and p type semiconductor layer, wherein, n N-type semiconductor N porous layer is deposited on the conductive substrates, semiconductor absorption layer evenly coats the nano grain surface of n N-type semiconductor N porous membrane, and the p type semiconductor layer is filled in the preceding two-layer space that stays.
N N-type semiconductor N porous layer is a mono-crystalline structures, so that electronics is expanded the energy level transmission according to the conduction band of n type layer, rather than crosses over the interface trap energy level of polycrystalline particle, the efficiency of transmission height of electronics.Adopt vertical orderly ZnO nano-stick array thin film, described ZnO nanometer rods diameter is the 50-100 nanometer, to satisfy the requirement to internal electric field and interior surface area; Interrod spacing should be the 80-150 nanometer, to satisfy the requirement to subsequent deposition space, internal electric field and absorptance; Rod length 100 nanometers-10 micron are to satisfy the extinction requirement.Synthesizing of n N-type semiconductor N ZnO nano-stick array thin film: adopt existing melten gel-gel spin coating technique and Liquid to prepare the ZnO nano-stick array thin film.
Semiconductor light-absorption layer CuInS
2Or CuInSe
2Between thickness 15-25 nanometer,, guarantee enough carrier separation efficient simultaneously to reduce the tunnelling recombination probability.Semiconductor light-absorption layer thickness has good uniformity, reduces the zone of thickness below 10 nanometers as far as possible, will reduce photogenerated current density greatly otherwise tunnelling is compound.Semiconductor light-absorption layer (ETA) film-forming process: continue to use existing liquid phase method film technique, realize that with liquid-phase chemical reaction a kind of material is the chemical industry common technology at another material surface uniform deposition.Only need light-absorption layer thickness (15-25 nanometer) as thin as a wafer in the ETA battery, and need the 2-3 micron unlike hull cell.Electronics and hole transport speed are not subjected to the crystalline quality of light-absorption layer or the influence of charge carrier diffusion length.It is fully feasible adopting liquid phase method prepared light-absorption layer like this and being applied to the ETA battery.
The p type semiconductor layer is CuSCN, should have preferably hole conductivity and the densification of remaining space is filled, to reduce the internal resistance of battery.The electrochemical deposition and the filling thereof of p type CuSCN semiconductive thin film: preparation and the densification in porous layer thereof of adopting present electrochemistry (or plating) deposition technique and hydrothermal technique process combined to finish p type CuSCN film are filled.
By the growth and the depositing operation of the three-decker of developing previously, assemble out ETA battery sheet, and finish the photoelectric properties of test battery, under the experiment condition condition, finish monocell sheet (2 * 2cm
2) photoelectric conversion efficiency be 11%; The efficient of single battery sheet can reach 10% under the working condition, and the efficient of battery pack sheet can reach 8%, can satisfy industrialized requirement.
Battery pack sheet line, encapsulation.
Claims (1)
1. inorganic thin film absorbed layer solar cell, comprise n N-type semiconductor N porous layer, semiconductor light-absorption layer and p type semiconductor layer, wherein, n N-type semiconductor N porous layer is deposited on the conductive substrates, semiconductor absorption layer evenly coats the nano grain surface of n N-type semiconductor N porous membrane, the p type semiconductor layer is filled in the preceding two-layer space that stays, it is characterized in that, described n N-type semiconductor N porous layer is a mono-crystalline structures, adopt vertical orderly ZnO nano-stick array thin film, described ZnO nanometer rods diameter is the 50-100 nanometer, and interrod spacing should be the 80-150 nanometer, excellent length 100 nanometers-10 micron; Described semiconductor light-absorption layer CuInS
2Or CuInSe
2Between thickness 15-25 nanometer, thickness is even; Described p type semiconductor layer is filled for the CuSCN densification.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101055900A (en) * | 2006-04-10 | 2007-10-17 | 上海太阳能科技有限公司 | Silicon solar battery |
| CN101132028A (en) * | 2006-08-25 | 2008-02-27 | 通用电气公司 | Single conformal junction nanowire photovoltaic devices |
| WO2009006910A2 (en) * | 2007-07-09 | 2009-01-15 | Tallinn University Of Technology | Photovoltaic cell based on zinc oxide nanorods and method for making the same |
| CN101692464A (en) * | 2009-07-09 | 2010-04-07 | 云南师范大学 | Cascade solar cell with nano rod array optical coupling element |
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2010
- 2010-05-10 CN CN2010101677872A patent/CN102244115A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101055900A (en) * | 2006-04-10 | 2007-10-17 | 上海太阳能科技有限公司 | Silicon solar battery |
| CN101132028A (en) * | 2006-08-25 | 2008-02-27 | 通用电气公司 | Single conformal junction nanowire photovoltaic devices |
| WO2009006910A2 (en) * | 2007-07-09 | 2009-01-15 | Tallinn University Of Technology | Photovoltaic cell based on zinc oxide nanorods and method for making the same |
| CN101692464A (en) * | 2009-07-09 | 2010-04-07 | 云南师范大学 | Cascade solar cell with nano rod array optical coupling element |
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Application publication date: 20111116 |