storage battery, secondary cell, or accumulator is a type of electrical battery which can be charged, discharged into a load, and recharged many times, as opposed to a disposable or primary battery, which is supplied fully charged and discarded after use.
In order to introduce cadmium telluride thin film solar Storage battery, environmental protection has to be included.Like many new industrial products, environmental protection is also a problem to be considered in the development of thin film solar Storage battery [ 91 ].Since environmental protection is a public sensitive topic, a lot of research has been done in this direction, and it is highly recommended that interested readers refer to [ 92 ] and the references therein.
Cd is a by-product of Zn production, with abundant sources and large-scale industrial applications.Although CD is toxic, water-insoluble CD compounds are not too toxic.It is necessary to take all possible measures to prevent the CD from entering the ecological environment and taking or sucking the CD into the human body.Risk assessment should be carried out in four stages of the life cycle of cadmium telluride thin film solar Storage battery and preventive measures should be taken [ 93 - 98 ]:
Mining and producing CdTe and CdS materials;
Production of cadmium telluride thin film solar cell module;
The service life of components after installation is longer than 20 years;
Demolition, disposal and recovery of components after their useful lives have expired.
The toxicity of compound semiconductor materials of different thin film solar Storage battery can be found in reference [ 99 ].Although CD is the parent element of CdTe and CdS, CdTe and CdS are insoluble in water and have low volatility.The harm caused by human body photographing is limited.The NREL of the US Renewable Energy Laboratory and the Brookhaven National Laboratory ( BNL ) of the US conducted toxicological studies on CdTe compounds [ 1 ] at the same time as the research and development of CdS thin film solar Storage battery.
Zinc ore contains about 0.25 % CD, so the annual CD production is tens of thousands of tons [ 92 ].If CD is not used by industry, it will be disposed of as hazardous waste.At present, more than half of the CD is used in rechargeable batteries, while the rest is used in dyes, plastic stabilizers, electroplating and soldering.Even the annual production of cadmium telluride thin film solar Storage battery on the order of GWP is less than 1 % of CD consumption.
The leading manufacturers of cadmium telluride thin-film solar Storage battery, First Solar / 1Q1 in the United States and Antesolar Regenergy in Germany, have well documented health problems in production.Dealing with toxic materials can be said to be a common problem encountered in industrial production. The production of cadmium telluride thin film solar Storage battery also requires appropriate safety rules and protective measures. The aspects that have received special attention include:
The elaborate design of the manufacturing plant;
Strict control of production equipment;
Long - term monitoring of the working environment;
Medical examination of operators.
Although there is no explicit legal requirement for the degree of exposure of hazardous materials in the factory, first solar conducted a long-term medical examination on the operators, which confirmed that CD levels in blood and urine samples can always be far below the threshold level.Practice has proved that designing and operating a factory with zero CD emission is technically and economically feasible. During the operation of cadmium telluride thin film solar Storage battery in their service life, the most likely environmental pollution risk comes from fire risk and leaching - out of damaged components.In a typical residential fire, the ambient temperature can reach 8001000 C, but the CD compound will not be released, because the CdTe and CdS gas pressures laminated and encapsulated in molten glass at such temperatures are very low. Leaching refers to the process of precipitating a certain component in a material with water or other solvents.For cadmium telluride thin-film solar Storage battery and copper indium gallium selenium thin-film solar Storage battery, people have studied the problem of leaching hazardous materials from damaged components [ 1 3 ], but the measured concentration in each case is lower than the tolerable concentration limit.
According to the current law, components that have ended their service life or are damaged can be treated as harmless waste as long as they meet the leaching standards.However, cadmium telluride thin-film solar cell manufacturers do not advocate disposing of waste components by landfill, but instead design recovery schemes for damaged components and production debris:
Re - enter production.
Other research directions
The active layer of a real cadmium telluride thin film solar cell cannot achieve absolute material purity, but people hope to control the impurity concentration to an acceptable level as far as possible.The source of impurities, in addition to the substrate, active layer and packaging material, will also come from various process steps:
Pollution of evaporation sources;
a side wall or device of the vacuum chamber;
Chemical water bath deposition of CBD;
Overall processing and storage._ Even if the CdTe precursor used in most laboratories is 5N or 6N purity, i.e. the relative amount of impurities is less than 10 - 6, the CdTe layer cannot be guaranteed to be nearly pure.However, the usual impurity concentration is very high, reaching 101710 I9CNR 3 [ 11 ].Due to the effect of self - compensation, such impurity concentration is much lower than the electrical activation concentration.Up to now, it has not been possible to strictly distinguish between beneficial impurities and harmful impurities.The specific impurity concentration also depends on production cost and process control.The purity determined by the appropriate impurity concentration is still worthy of continuous research and development.
At the current production level, the thickness of CdTe film is still 510 FUN, however, the thickness of 1 - 2 is enough to make the Storage battery work well, but too thin a Storage battery will also slightly reduce the response of the infrared light band.The existing Storage battery thickness level makes the material utilization rate and deposition rate lower and the production cost higher.However, thinner or more empty films will reduce the yield of production, which is especially serious when wet etching process is used.Therefore, the thickness of CdTe film cannot be too thin when the production technology cannot guarantee a tight and closed CdTe film.Some experimental work on thin absorption layer has been carried out [ 62' 1 ( ) 4 ], and the influence of CdTe layer thickness on ideal Storage battery has also been theoretically studied through numerical modeling [ 89 ].
If the thickness of the CdTe layer is further reduced below 100 nm, the concept of a planar cell will not allow CdTe to absorb enough incident light, but will require the concept of an ETA cell with an extremely thin absorption layer.The porous window layer material used in ETA Storage battery is usually TiO 2, while a very thin CdTe layer permeates into TiOP 5 - 1OT.
In the description of polysilicon thin film solar Storage battery in chapter 3, it was clarified that " polysilicon" refers to polycrystallineilicon with a grain size of 0.1 fxm 1 mm, rather than multicrystallineilicon with a grain size of 1 mm 10 cm for polysilicon solar Storage battery.The polycrystalline CdTe structure in cadmium telluride thin film solar Storage battery is also poly crystal, with grain size on the order of LMM and depending on different technologies.The description of grain boundary effect of CdTe polycrystalline structure can be found in reference [ 17 ].The cadmium telluride thin film solar cell and the copper indium gallium selenium thin film solar cell are also collectively referred to as polycrystalline thin film solar Storage battery.
The grain size on the household scale will determine the characteristic length of several cadmium telluride thin film solar Storage battery, making them also close to the order of 1fx m:
Absorption length ( absorption length, 1 / a );
minority diffusion length Ln;
Depletion width ( w ) o
Therefore, the influence of grain structure on Storage battery performance is obvious.Sites et al quantitatively estimated the influence d of polycrystalline structure and compared single crystal GaAs with polycrystalline CdTe.The two materials have the same band gap, i.e. = 1.45 eV, and in principle should have the same photovoltaic application potential.However, the laboratory conversion efficiency of gallium arsenide solar Storage battery was recorded as 25.7 %, while that of cadmium telluride thin film solar Storage battery was only 16.5 %, a difference of 9.2 %. More than half of this difference is due to several effects of CdTe polycrystalline structure that can distort the band diagram near grain boundaries:
Charged interface states;
Increase or decrease of doping concentration near grain boundary inside grain;Diffusion and segregation of impurities at grain boundaries;
Material modification at grain boundaries.
Under certain conditions, grain boundaries will become channels for diffusion of various elements [ 11' 1113, substrate: Na;
TCO Window Layer: In;
CDS buffer layer: S;
Contact electrodes: Te, Cu, Sb.
The influence of grain boundaries on the characteristics of the final Storage battery can be discussed by energy band diagram.Actually. 7 does not consider the grain boundary structure containing other materials, otherwise the band gap at the grain boundary is different from that in vivo.To sum up, the actual grain boundary structure of .7 and passivates the electron recombination at the grain boundary, which is beneficial to photovoltaic effect.However, the actual grain boundary structure of .7 will increase the electron recombination at the grain boundary, which is not conducive to photovoltaic effect.However, the details of carrier concentration, recombination and transport are very complex and obviously depend on the height of the grain boundary barrier and the two-dimensional geometry of the transverse or longitudinal grain boundaries.Visoly - Fisher and others pointed out that the grain boundary structure with band bending larger than the actual value of .7 is a low recombination path, which is helpful for electron transport, but this view requires quantitative confirmation [ 118 ].
Advanced Storage battery structure
The cadmium telluride thin-film solar Storage battery we discussed are also " upper - layer configurations".In space applications, the power-to-weight ratio is an important quality factor, and heavy glass substrates need to be replaced by thin sheets.If a transparent plastic sheet is used, the upper layer configuration can be maintained.However, the plastic material needs to be exposed to the high temperature at which CdTe is prepared.
Opaque foil can be used in " substrate configuration".
The research and development team of Switzerland Zurich Institute of Technology ( ETHZ ) has solved the problem of the upper layer configuration of plastic films, spin-coating and peeling on reusable glass substrates, and realizing the upper layer configuration on a 10 - thick polyimide sheet with a conversion efficiency of 11.4 % [ 129,13 ].The purpose of developing this advanced Storage battery concept is space application and can also be applied to building integration.
Cadmium telluride thin-film solar Storage battery have good radiation protection [ 131,132 ], far better than crystalline silicon solar Storage battery or arsenic-doped solar Storage battery, and even better than copper indium gallium selenium thin-film solar Storage battery to some extent.The reason why cadmium telluride thin film solar Storage battery have better radiation resistance is relatively simple.Only when the number of defects induced by electron and proton radiation exceeds the number of defects existing in Y just after the Storage battery was prepared will the performance of the Storage battery begin to decay.The performance of a crystalline silicon solar cell depends on a larger minority carrier diffusion length' and its cell thickness is 100 times greater than that of a thin film solar cell, so its trap density tolerance range is 103104 times lower than that of a thin film solar cell.As a result, the radiation condition that attenuates the performance of thin film solar Storage battery is several orders of magnitude higher than that of crystalline silicon solar Storage battery or arsenic-doped solar Storage battery.The comparison of radiation attenuation of different materials can be found in the actual reference [ 132 ]
Another research direction worthy of attention is to further develop back contact technology.Through special CdTe surface treatment, ohmic contact of N + TCO can be realized on P - type CdTe [ 13.Such a Storage battery structure has two transparent contact electrodes and can be designed for use as a double-sided Storage battery or a laminated Storage battery.Some research and development efforts have attempted to replace the wet etching step in the existing process, i.e. CdTe surface treatment before deposition of the contact electrode structure, while the alternative technology is dry vacuum process [ 134 ].Recently, a complete " dry" cell ( DRY cell household 7.4 cadmium telluride thin film solar cell ) process has been implemented
Sublimation in Near Space
At present, the two leading cadmium telluride thin-film solar cell companies, namely, Germany's ANTECSOLERGY and the United States' First Solar, have both deposited CdTe absorbing layers by sublimation technology.Sublimation is a phase change process in which a substance changes from a solid phase to a gas phase without undergoing a liquid phase. This endothermic phase change process requiring specific temperature and pressure conditions is lower than the three-phase point in the phase change diagram.The near-space sublimation ( CSS ) technique used by AntecSolar has deposited about 0.10.2 thick CdS layer and about 510 thick CdTe layer ⑽.In the CSS process, the mutual spacing distance between the deposition source and the substrate is short, specifically 1 mm number cm, and depends on the size of the substrate.CSS deposition conditions are low vacuum, specifically 0.11 Pa or 1 ( T310 - 2 mbaro deposition source and substrate need to be heated to a high temperature in the range of 500 C, and the temperature is monitored in situ by thermocouples, while the temperature of the deposition source needs to be slightly higher than that of the substrate.The deposition source may be in the form of a tablet, granule or powder of CdTe compound.The mixing ratio of CD and TE powder needs to be stoichiometric.The driving force of CSS deposition is the temperature difference between the deposition source and the substrate and the surface energy of the substrate.According to solid physics, the energy on the surface of an object is higher than that in the body, and this part of the energy is the surface energy.In CSS deposition, the surface energy of the substrate depends on its composition, crystalline state and morphology.
In fact. 9 gives an illustration of batch CSS deposition equipment, and there are many derivatives of this technology.The inert carrier gas Ar or N2 can be used at 100Pa or LM bar, even at atmospheric pressure.This sublimation technique is sometimes referred to as near-space gas transport CSVT, which can deposit not only CdTe but also CdS.
CdTe can be said to be a " tolerant" material to deposition techniques and preparation conditions. Various deposition techniques can successfully prepare CdTe layers of device quality.The properties of CdTe materials seem to depend more on the CDC L2 activation process.rather than the deposition process itself.This phenomenon has stimulated the research and development of many low-cost deposition technologies. The next section will introduce the non-vacuum deposition technology of CdTe, and here we will discuss various vacuum deposition technologies first:
Evaporation: U.S. Universityofdelaware team prepared CDS / CdTe batteries with conversion efficiency over 10 % using traditional vacuum evaporation [ 119 ].
Stacked Element Layer ( SEL ): Evaporate CD thin layer and TE thin layer successively, and then anneal to obtain CdTe layer [ 12 ].
Atomic layer deposition ALD: if the continuous element layer of SEL is effectively confined to a single atomic layer.This deposition technique was originally called atomic layer epitaxy ( ale ), but now called atomic layer deposition ( ALD ) o the method of depositing CD and te monatomic layers is to periodically change the gas flow rate containing CD and te inert carrier gases.The inorganic precursor gas source also sometimes uses CDC L2.ALD technology can well control the CDS / CdTe mixed region and can limit the number of atomic layers to any number.ALD technology has achieved a high conversion efficiency of 14 % CDS / CdTe solar cell [ 121 ].
Metal Organic Chemical Vapor Deposition MOCVD: In MOCVD, the precursor of vapor deposition CdTe is metal organic compounds such as Cd2 and 2CHTE.Both gases are simultaneously applied to the substrate.The characteristics of CdTe thin films are controlled by process parameters such as gas temperature, gas flow rate, precursor concentration and substrate temperature. This technology is suitable for industrial mass production and has been successfully applied to CdS layer, CdTe layer " 122,12" and back contact structure ( see section 7.3.2 ).
Non - vacuum technology
Compared with near-space sublimation CSS and other vacuum deposition technologies, the advantage of non-vacuum technology is lower production cost.
Electroplating: U.S. BP Solar first developed the electroplating process of cadmium telluride thin film solar Storage battery to the industrialization level " 124 \ Electroplating can deposit CdS and CdTe layers at lower temperatures, followed by heat treatment at temperatures higher than 400 C ..
Chemical water bath deposition of CBD: dipping the substrate in an aqueous solution containing Cd2 + and S2 - ions, such CBD technology is widely used in the process of preparing CDS buffer layer for copper indium gallium selenium thin film solar Storage battery.CBD can also prepare closed CdS buffer layer E - with very thin thickness for cadmium telluride thin film solar Storage battery.However, due to the limited thickness of CBD deposited film, this technique is not suitable for depositing CdTe absorbing layer.
Solution Spraying: The aqueous solution used for solution spraying contains CD precursors.The aqueous solution is sprayed on the heated substrate to form CdTe compound on the substrate, and the residue volatilizes, thus realizing the process of preparing CdTe absorbing layer by solution spraying.The first to develop the process of solution spray deposition of CdTe layer was the U.S. Phototon Energy, later Golden Phototon, which achieved 12.7 % cell conversion efficiency [ 125' 126 ].
Screen printing and sintering: Japan's Panasonic Storage battery has developed the technology of screen printing and sintering to the advanced industrial level [ 45,127 ].Seoul University El28 in South Korea and Ghent University in Belgium [ 43' 78 ] have also made many contributions to this technology [ 43, 78 ].The screen-printed slurry contains CdS or CdTe powder, while a certain proportion of CdCs L2 powder plays a role of dilution.After screen printing and dehydration, the substrate was sintered at 500 600 C in N2 atmosphere.Screen printing and sintering process can obtain a thicker film with a thickness of 10 - 30 households and a larger grain size. Finally, the conversion efficiency of cadmium telluride thin film solar Storage battery can reach up to 12 %.
The unique advantage of thin-film solar Storage battery is to integrate and interconnect the Storage battery, i.e. monolithic integration, laser scribing or mechanical scribing to realize automatic production of the fabricated components.The deposition of each layer of thin film can be carried out at the full assembly size.After the transparent conductive oxide TCO is deposited on the substrate, the first scribe H is performed over the entire width of the substrate.The width of the scribed lines should be as narrow as possible, generally reaching the range of 100, and it is necessary to avoid leaving behind TCO materials to prevent local shunting paths' the mutual spacing of the scribed lines needs to be on the order of 510 mm according to the optimized graphic design ( see 220.127.116.11 Section ).After the first scribing h with isolation effect on the surface of TCC, CDs buffer layer, CdTe absorption layer sinking and CdCl2 activation are successively performed, and then the second scribing with connection effect is performed on the CDs layer and CdTe layer, with P2 reaching the depth of TCO layer surface.Because the TCO layer is harder than the semiconductor layer and has stronger adhesion, it is completely feasible for P2 to accurately reach the surface of the TCO layer.After P2, the substrate is metallized to prepare a back contact so that adjacent isolated Storage battery are connected in series with each other.The last third score P3 can isolate the back contact of adjacent Storage battery.Integrated interconnection technology can automate the production of 60 cmx 120 cm components with a high production rate [ s' 12 ] of only 2 min per component.
At present, the industrialization of cadmium telluride thin-film solar Storage battery is continuously advancing.
On the production line 5' 136 ] of Antecsolarengy in Germany, transparent conductive oxide TCO was prepared by sputtering, while CdS buffer layer and CdTe absorption layer were deposited by near-space sublimation CSS.The same production line can integrate these two process steps, as well as all process steps such as CdTe activation processing, sputtering deposition of metal contact electrodes, contact electrode processing, laser scribing integration interconnection, etc.The module size is 60 cmx 120 cm, the production rate is 2 min per module, and the capacity is 100000 m2 / a, which is equivalent to 8 mwp / a capacity of 8 % of the current conversion efficiency.In the second production line, the final assembly is sealed with glass plates. The actual production cost is less than 2 / WP and the energy recovery period is less than 1 year ( lighting conditions in central Europe ).
U.S. First Solar uses the same component size 137 as AnthecSolar, but the average conversion efficiency of components reached 11 % in 2010.The deposition of CdS layer and CdTe layer adopts high-rate vapor deposition ( HRV TD ), and CdS or CdTe is sublimated into vapor deposition on the substrate, which is a derivative technique of CSS deposition.The annual production capacity in 2003 is only 3m wp / a, while the production bases in the United States, Germany and Malaysia have a total production capacity of 1.43 GWP / a in 2010, and it is planned to expand the production base to France and Vietnam to reach a production capacity of 2.74 GWP / a in 2012.In February 2009, the cost of its cadmium telluride thin film solar cell module exceeded the $ 1 / WP threshold.In the third quarter of 2010, the cost reached $ 0.77 / WP;First Solar hopes to reach a component cost of $ 0.520.63 / WP by 2014 by improving component conversion efficiency and capacity.At present, First Solar occupies 40 % of the U.S. solar power market._ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Actual.4 First Solar's annual capacity in the United States can develop _ _ _ _ _ capacity by 8 MWP / A ) 200520062008200920112012 U.S. 2599132143160238238238 Germany 1761921214238477477 Malaysia 38285414301430 France 119 Vietnam 238 total capacity 251003808712281431462742 Currently, Calyxo, a subsidiary of German Q - Cells, Prime Star Solar, Italian Arendi and U.S. Aboundsolar are all developing and producing cadmium telluride thin film solar Storage battery.In December 2010, AboundSolar announced that the U.S. production base will reach 640 MWp / a capacity by 2012, which will exceed First Solar's capacity in the U.S. mainland.
Japan Matsushita Storage battery uses screen printing and sintering processes to prepare cadmium telluride thin film solar Storage battery, which meet the indoor application market, such as Panasonic calculator 1273.Although Panasonic's Storage battery technology has developed to a considerable extent, its operation of cadmium telluride thin film solar Storage battery ended in 2002.The U.S. BP Solar used electroplating technology to prepare cadmium telluride thin film solar Storage battery, and reached the equivalent technical level [ 124 ], with the conversion efficiency of large-area components exceeding 10 %. It also installed a 10 MWP power station in Fairfield, California, U.S., but stopped related business in 2002.
In the process of industrialization of high-tech products, the company's business activities are often very active. It is normal business behavior to start, restructure, merge and withdraw.For more information on the industrialization of cadmium telluride thin film solar Storage battery, please refer to [ 12 ].
Physical Characteristics and Numerical Modeling of Thin Film Solar Cells in Crushing Pot 7.5.1 Relationship between Physical Characteristics and Numerical Modeling
Cadmium telluride thin film solar Storage battery have complex polycrystalline structures, and many material parameters, operation mechanism and performance phenomena cannot be directly described by classical semiconductor physics.However, numerical modeling is a very useful theoretical analysis method, which can explain the experimental results to a great extent and give ways to optimize the Storage battery performance.Modeling of physical problems needs to be based on certain assumptions and simplification of related problems.In order to accurately and quantitatively describe the performance of thin film solar Storage battery, numerical simulation is essential.Such numerical simulation often needs to consider a large number of parameters, at least 50, and it is obviously impossible to calculate all 50 parameters as independent variables.This means that some definite parameters from experimental results and structural design need to be input into the numerical simulation, so we can say that the physical characteristics of cadmium telluride thin film solar Storage battery are closely related to the numerical modeling.Selecting a set of appropriate parameters to simulate the experimental results is not a job that can be left to the computer, but rather requires considerable physical intuition.Some simple " submodels" are proposed to help numerical analysis of the approximate characteristics of local parameters ( e.g., the parameters of back contact of cadmium telluride thin film solar Storage battery ) so as to guide physical intuition to make more accurate judgments.We will first briefly discuss the main physical characteristics of cadmium telluride thin film solar Storage battery, and then sort out these large numbers of parameters.Subsequently, we will discuss the numerical simulation of cadmium telluride thin film solar Storage battery from the " double diode" model describing back contact.
Theoretical Analysis of Physical Characteristics
Voltammetric characteristic curve can give four basic photovoltaic parameters:
Short circuit current density JSC;
Fill factor ff;
Conversion efficiency >
The volt-ampere characteristic curve of cadmium telluride thin-film solar Storage battery in the dark and in the light has two characteristics: because the contact resistance is the main factor, the incident light intensity needs to be changed at a specific temperature to record the short-circuit current density.and an open circuit voltage to obtain a human - VOE curve.If billion is not very large and the short-circuit current density and open-circuit voltage are less affected by it, the H - VOE curve will in principle only contain J _ V curve information without series resistance ruler in the dark.However, unlike crystalline silicon solar Storage battery, cadmium telluride thin-film solar Storage battery and other thin-film solar Storage battery do not have a simple shift of dark current curve under illumination.Therefore, the parameters of 72, person and AE measured by AE - VOE are different from those measured by J - V in the dark.This explains the so-called " dark diode current parameter measured under illumination" problem proposed in many literatures.In an ideal solar cell, the open circuit voltage decreases linearly with the temperature t.By extrapolating the straight part of the voe - t curve to t = 0k, the current mechanism of dark current formation can also be given.For various common current mechanisms, the expressions of n, human, △: and VM parameters are shown in actual .5 ..Among them, the P - type region is considered to have a low doping concentration.The recombination of quasi-neutral region ( QNR ) and space charge layer ( SCL ) is still the most important current mechanism.EGI and △ 3 are the interface band gap and conduction band dislocation defined in actual .3, respectively.Interface state energy level ( e, ), trap energy level ( trapenerggylevel ), and interface recombination velocity s: describe the influence of interface state and SCL non-band gap central defect on carrier recombination and dark current, respectively. the non-band gap central defect is relative to the band gap central defect.The power series expansion coth ( _ r ) is used to calculate the diode ideal factor n in barrier radiation and barrier penetration.+ search, < 1.These quantitative results of X6 results come from the summary of several literatures [ 16' 139' 14 ], and the conclusions given can be used as the basis for analyzing J - V curves and curves in the dark.Because the values of Z7 and A are correlated with each other, quantitative analysis needs to satisfy the self-consistent O - deep level transient spectrum DLTS and related techniques, which are not conventional semiconductor measurement techniques [ 41 ].DLTS is a semiconductor testing tool for studying electrically activated defects. It can measure defect density and other basic defect parameters in materials, and some parameters are considered as characteristic parameters for determining and analyzing related defects.In DLTS, the Storage battery is biased by a static reverse voltage before receiving a transient excitation, which can be any of the following.The investigation of lead removal by biosorption: an application at storage battery industry wastewaters
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