CN101411001A - Nanoparticle sensitized nanostructured solar cells - Google Patents

Nanoparticle sensitized nanostructured solar cells Download PDF

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CN101411001A
CN101411001A CN 200780011092 CN200780011092A CN101411001A CN 101411001 A CN101411001 A CN 101411001A CN 200780011092 CN200780011092 CN 200780011092 CN 200780011092 A CN200780011092 A CN 200780011092A CN 101411001 A CN101411001 A CN 101411001A
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layer
nano particle
photovoltaic device
nanostructure
hole transmission
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戴莫德·雷迪
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Solexant Corp
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Abstract

In general, the invention relates to the field of photovoitaics or solar cells. More particularly the invention relates to photovoltaic devices using metal oxide nanostructures in connection with photoactive nanoparticles including nanoparticles of different size and composition to form a photovoltaic device.

Description

The solar cell of nanoparticle sensitized nanostructure
Technical field
Substantially, the present invention relates to photovoltaic cell (photovoltaic cell) field or area of solar cell.More specifically, the present invention relates to use nanostructure and the nano particle that comprises different sizes and different component photovoltaic device with the photosensitive nanoparticles that forms photovoltaic device.
Background technology
Ever-increasing oil price has increased the importance of the regenerative resource to one's profit of developing the economy.Thereby the whole world is being carried out important effort and is being obtained solar energy with the solar cell of developing the economy to one's profit.Present heliotechnics mainly can be categorized as crystalline silicon and thin film technique.Solar cell above 90% is by silicon-monocrystalline silicon, polysilicon or amorphous silicon manufacturing.
In history, crystalline silicon (c-Si) has been used as the extinction semiconductor in most of solar cells, although it is relatively poor relatively absorber of light and the material that needs sizable thickness (hundreds of micron).Yet, it is proved to be easily, because it provide have good efficiencies (12-20%, half of theoretical maximum is to 2/3rds) stable solar cell and use the technology that from the knowledge base (knowledge base) of microelectronics industry, develops.
Crystalline silicon two types of industrial uses.First kind is monocrystalline silicon, and it is by making from highly purified monocrystal silicon (single crystal boule) cut crystal (approximately diameter and 350 micron thickness of 150mm).Second kind is polysilicon, and it at first cuts into rod (bar) by the ingot bar (cast block) with silicon and makes to wafer then.The main trend of crystal silicon cell manufacturing is that the direction to the polycrystalline technology develops.For monocrystalline silicon and polysilicon, by forming the semiconductor p-n junction in the top surface that phosphorus (n type alloy) is diffused into boron doped (p type) Si wafer.The contact of silk screen printing is applied to the front and rear of battery, and anterior contact patterns is designed to allow the light of maximum to be exposed to silicon materials and electricity (resistance) loss minimum in the battery especially.
Silicon solar cell is very expensive.Make ripe but can not bring significant cost to reduce.Silicon is not the ideal material that is used for solar cell, thereby because the visibility region that it mainly absorbs solar spectrum has limited conversion efficiency (conversion efficiency).
Second generation solar battery technology based thin film.Two kinds of main thin film techniques are amorphous silicon and CIGS.
Amorphous silicon (a-Si) is considered to only film photovoltaic (PV) material in the 1980s.But at that year end ten and in earlier 1990s and since its inefficient and unsteadiness it abandoned by many researchers.But amorphous silicon technology has obtained good progress on the solution of development to very complicated (sophisticated) of these problems: more piece structure (multijunctionconfiguration).Now, the efficient of Shang Ye more piece a-Si module can be in the scope of 7%-9%.The manufacturing facility of 25MW has been built in United Solar System Corporation and Kanarka plan, and several companies have announced the plan in Japan and Germany construction manufacturing works.The facility of 10MW is built in BP Solar and United Solar System Corporation plan in the near future.
The key obstacle of a-Si technology is inefficient (stable about 11%), photoinduction efficiency degradation (light-induced efficiency degradation) (this needs more complicated battery design, for example more piece) and technology cost (manufacture method is based on vacuum and quite slow).All these problems all are important to the potentiality of making cost-effective a-Si module.
The thin-film solar cells of being made by copper indium diselenide gallium (CIGS, Copper Indium Gallium Diselenide) absorber is hopeful to realize the high conversion efficiency of 10-12%.Compare by the efficient that other thin film techniques of for example cadmium telluride (CdTe) or amorphous silicon (a-Si) obtain with those, the high efficiency of the record of CIGS solar cell (19.2%NREL) is up to the present the highest.
These small-area devices that break a record have adopted capital intensive and very expensive vacuum evaporation technique manufacturing.The CIGS film of making even component on large-area substrate is very challenging.This restriction also has influence on common low-down process yield.Because these restrictions, evaporation technique be implemented in thin-film solar cells and module on a large scale, in the commodity production cheaply and unsuccessful and can't compete mutually with the crystal silicon solar module of today.
In order to overcome the restriction of the physical gas phase deposition technology that uses expensive vacuum equipment, the vacuum technology that several companies have developed high yield (for example: DayStar, Global Solar) and adopting non-vacuum process (for example: ISET Nanosolar) is used to make the CIGS solar cell.Adopt ink technology (inktechnology), can realize very high active material utilization (active material utilization) with relatively low capital equipment expense.And the effect of usefulness is the low-cost manufacturing process that is used for the thin film solar device.CIGS can make on flexible base, board, makes it can reduce the weight of solar cell like this.The cost expection of CIGS solar cell is lower than crystalline silicon, even make them also competitive under lower efficient.Two subject matters of CIGS solar cell are: (1) does not reach the approach clearly of greater efficiency; And (2) high treatment temperature makes it be difficult to adopt high-speed winding (roll toroll) technology, so they can not realize the structure of lower cost significantly.
These are prominent questions that current available techniques exists.Have greater than the crystal silicon solar energy battery of 90% the market share very expensive now.Utilize the expense of the crystal silicon solar energy battery of solar energy to be approximately 25 cents/kilowatt hour, fossil fuel by comparison is less than 10 cents/kilowatt hour.In addition, it is very high and limited its utilization rate (adoption rate) capital cost (capital cost) of solar panels (solar panel) to be installed.Crystalline solar cell technology is ripe, unlikely improves the competitiveness of performance or cost in the near future.Amorphous silicon thin film technology is suitable for realizing a large amount of manufacturings, and this can obtain solar cell cheaply.In addition, amorphous silicon and microcrystalline silicon solar cell only absorb in visibility region.
Solar cell of future generation need be realized high efficiency and light weight and low cost veritably.Two potential candidates are (1) polymer solar battery and (2) nano particle solar cell.Because the winding process under moderate temperature (＜150 ℃), polymer solar battery has potentiality cheaply.But polymer has two main shortcomings: the poor efficiency that (1) causes owing to charge transfer slowly; And the stability of (2) difference-especially to ultraviolet light (UV).Therefore can to realize becoming the required performance of solar cell of future generation be unlikely to polymer solar battery.The most promising technology that is used for solar cell of future generation is based on quantum dot (QD, quantum dot) nano particle.
The experimental study of the solar cell that several research groups have carried out quantum dot-based (quantum dot based).Most of normally used quantum dots are by making such as the compound semiconductor of II-VI, II-IV and III-V family.Some examples of these photosensitive quantum dots are CdSe, CdTe, PbSe, PbS and ZnSe.
The solar cell of being made by described photosensitive nanoparticles in the art shows low-down efficient (＜5%).When being exposed to sunlight, nano particle produce the electron hole electric charge to aspect very effective.These inefficient main causes are charge recombination (charge recombination).In order to realize high efficiency in solar cell, electric charge must separate when producing at them.Thereby compound electric charge does not produce the efficient not contribution of any photoelectric current to solar cell.Charge recombination in the nano particle is mainly due to two factors: (1) promotes the surface state of charge recombination on nano particle; And (2) charge transfer slowly.In the situation of back, because electric charge is lentamente by electron transfer layer and hole transmission layer, so charge recombination is compared usually faster with charge transfer speed.
Reported that in the prior art the whole bag of tricks is to solve these problems of nano particle.Process for treating surface is attempted removing surface state.(seeing Furis et al., MRS Proceedings, volume784,2004) these technology have shown the improvement aspect luminescence generated by light but can not improve solar energy converting efficient, because they do not influence the charge transmission of hole transmission layer and electron transfer layer.
As known in the artly be: TiO 2Layer can be used in transmission electronic fast.Dye sensitization (dye-sensitized) solar cell uses TiO 2It is exactly this reason.Transparent TiO 2Nanotube be in the news in the literature (Mor et al., Adv.Funct.Mater., 2005,15,1291-1296 (2005)).These TiO 2Nanotube has been used to prepare the solar cell of dye sensitization.
Summary of the invention
Photovoltaic device comprises first electrode and second electrode, and at least one in these two electrodes is transparent to solar radiation.The ground floor and first electrode conductance that comprise the electron conduction nanostructure are logical.The photoactive layer that comprises photosensitive nanoparticles is positioned near the electron conduction nanostructure.Hole transmission layer contacts with second electrode with photoactive layer.Also can be included in the barrier layer between the hole transmission layer and first electrode.
The electron conduction nanostructure can be nanotube, nanometer rods or nano wire.Preferred nanotube is by TiO 2Make.Preferred nano wire is made by ZnO.
Photosensitive nanoparticles can be quantum dot, nanometer rods, nanometer bipod, nanometer tribrach, nanometer multiway platform or nano wire.In some cases, photosensitive nanoparticles is covalently attached to nanostructure.Preferred photosensitive nanoparticles comprises CdSe, ZnSe, PbSe, InP, PbS, ZnS, Si, Ge, SiGe, CdTe, CdHgTe or II-VI, II-IV or III-V family material.In certain embodiments, in photovoltaic device, use first nano particle and second nano particle of absorption from the radiation of the different piece of solar spectrum.First nano particle can be different in the combination of component, size or size and composition with second nano particle.
In another embodiment, second photoactive layer of use contains and compares the nano particle of absorption from the radiation of the different piece of solar spectrum with the nano particle of ground floor.Can be different in the combination of composition, size or size and composition at first photoactive layer and the nano particle in second photoactive layer.
In certain embodiments, hole transmission layer is the hole transport polymer (conducting polymer) such as p N-type semiconductor N polymer.The example of p N-type semiconductor N polymer comprises P3HT, P3OT, MEH-PPV or PEDOT.In other embodiment, hole transmission layer is the p N-type semiconductor N.The example of p N-type semiconductor N comprises the Ge of Si, the p doping that p mixes or the SiGe that p mixes.Under the situation of Si, the p N-type semiconductor N can be the microcrystal silicon of p doped amorphous silicon, p doping or the nanocrystal silicon that p mixes.In some cases, hole transmission layer is made by two-layer or multilayer p N-type semiconductor N.The p type semiconductor layer can be silicon layer, the germanium layer of p doping and/or the SiGe layer that p mixes that p mixes.
Photovoltaic device can comprise that the ground floor of electron conduction nanostructure makes the ground floor and first electrode conductance lead to and makes by formation on first electrode.Then, the photoactive layer that comprises photosensitive nanoparticles is formed on the electron conduction nanostructure.Then, hole transmission layer is formed on the photoactive layer.Second electrode is based upon on the hole transmission layer then.In first electrode and second electrode at least one is transparent to solar radiation.Before nanostructure or hole transmission layer formation, also can incorporate the barrier layer into.Can adopt different nano particles to make photoactive layer in this layer, to produce the random distribution of different nano particles.In another embodiment, photoactive layer is made by two-layer at least different nano particle.Under this situation, this method is included in layer that forms first nano particle on the nanostructure and the layer that forms second nano particle on the layer of first nano particle.
Description of drawings
Fig. 1 (prior art) illustrates the nano-quantum point that absorbs and launch the different size of the radiation with different colours.Point absorbs and large-sized red end absorption at spectrum at the indigo plant end of spectrum.
Fig. 2 (prior art) illustrates the absorption respectively/emission UV that is made by ZnSe, CdSe and PbSe, the quantum dot of visible and infrared (IR).
Fig. 3 (prior art) illustrates by coated with such as trioctyl-phosphine oxide (tri-n-octyl phosphineoxide, the nano particle of solvent TOPO).
Fig. 4 illustrates the nano particle with R base functionalization.The R base can be used X a-R n-Y bExpression, wherein X and Y are such as carboxylic acid (COOH) base, phosphoric acid (H 2PO 4) basic, sulfonic acid (HSO 3) reactive group of base or amine, a and b are 0 or 1, and wherein one of a and b are 1, and R is carbon, nitrogen or oxygen, and n is 0-10 or 0-5.
Fig. 5 A-5F illustrates the formation according to the solar cell of an embodiment.In Fig. 5 A, the titanium thin film deposition is on the tin oxide that the fluorine that is deposited on the transparency carrier mixes.In Fig. 5 B, the TiO on the tin oxide that fluorine mixes 2Nanotube deposition is on transparency carrier.In Fig. 5 C, have the TiO of hydroxyl functional base 2Nanotube deposition is on the tin oxide that the fluorine that is deposited on the transparency carrier mixes.In Fig. 5 D, nanoparticle sensitizer is attached to TiO 2Nanotube.In Fig. 5 E, be deposited upon on the nanoparticle sensitizer such as the transparent hole transport of ITO, PEDOT etc.In Fig. 5 F, electrode layer (ITO or metal) is deposited on nanoparticle sensitized TiO 2On the nanotube, the TiO that this is nanoparticle sensitized 2Nanotube is on the tin oxide that the fluorine that is deposited on the transparency carrier mixes.
The nanoparticle sensitized solar cell that Fig. 6 illustrates among Fig. 5 F receives sunlight (100) to produce voltage.
Fig. 7 illustrates and has titanium metal foil (metal foil) another embodiment as the nanoparticle sensitized solar cell of substrate and electrode.
Fig. 8 illustrates the TiO that has on the tin oxide that fluorine mixes 2The nanoparticle sensitized solar cell of nanometer rods.
Fig. 9 illustrates the TiO that has on titanium metal foil 2The alternative of the nanoparticle sensitized solar cell of nanometer rods.
Figure 10 illustrates the embodiment in the broadband (broadband) of the solar cell of Fig. 6, and wherein the quantum dot of different size and/or component is randomly dispersed in TiO 2On the nanotube.
Figure 11 illustrates the broadband embodiment of the solar cell of Fig. 7, and wherein the quantum dot of different size and/or component is randomly dispersed in TiO 2On the nanotube.
Figure 12 illustrates the broadband embodiment of the solar cell of Fig. 9, and wherein the quantum dot of different size and/or component is randomly dispersed in TiO 2On the nanotube.
Figure 13 illustrates the broadband embodiment of the solar cell of Fig. 8, and wherein the quantum dot of different size and/or component is randomly dispersed in TiO 2On the nanotube.
Figure 14 illustrates the broadband embodiment of the solar cell of Fig. 6, and wherein the quantum dot layer of different size and/or component is positioned at TiO 2On the nanotube.
Figure 15 illustrates the broadband embodiment of the solar cell of Fig. 7, and wherein the quantum dot layer of different size and/or component is positioned at TiO 2On the nanotube.
Figure 16 illustrates the broadband embodiment of the solar cell of Fig. 8, and wherein the quantum dot layer of different size and/or component is positioned at TiO 2On the nanotube.
Figure 17 illustrates the broadband embodiment of the solar cell of Fig. 9, and wherein the quantum dot layer of different size and/or component is positioned at TiO 2On the nanotube.
Embodiment
The embodiment of photovoltaic device disclosed herein by two electrodes, comprise the electron conduction nanostructure ground floor, comprise photosensitive nanoparticles nearby electron electrical-conductive nanometer structure photoactive layer and the contact photoactive layer hole transmission layer form.The ground floor and first electrode conductance are logical.The hole transmission layer contact photoactive layer and second electrode.In first electrode and second electrode at least one is transparent to solar radiation.
As used herein, term " nanostructure " or " electron conduction nanostructure " expression nanotube, nanometer rods, nano wire etc.The electron conduction nanostructure is crystal in essence.Usually, nanostructure is made by the semi-conducting material of broad-band gap, and wherein band gap is for example TiO 23.2eV.Select nanostructure make they band gap greater than the band gap of the maximum that will be used in the photosensitive nanoparticles in the solar cell (for example,＞2.0eV).
The electron conduction nanostructure can be made by for example titanium dioxide, zinc oxide, tin oxide, indium tin oxide (ITO) and indium-zinc oxide.Nanostructure also can be made by other the electric conducting material such as carbon nano-tube.Nanostructure can be grown directly upon metal forming (metal foil), glass substrate scribble the conducting metal of the thin tin oxide that mixes such as fluorine or the plastic base of metal oxide film on.For TiO 2Nanostructure is seen for example Mor et al., " Use of Highly-Ordered TiO 2NanotubeArrays in Dye-Sensitized Solar Cells. " Nanoletters Vol.6, No.2, pp.215-218 (2005) .Mor et al., Nanoletters Vol.5, no.1, pp.191-195 (2005); Barghese et al., Journal of Nanoscience and Nanotechnology, no.1, Vol.5, pp.1158-1165 (2005); And Paulose et al.Nanotechnology 17, pp.1-3 (2006).For the ZnO nano wire, see Baxter and Aydel, Solar Energy Material and Solar Cells 90,607-622 (2006); Greene, et al., Angew.Chem.Int.Ed.42,3031-3034 (2003); And Law, et al., Nature Materials 4,455-459 (2005).
Can prepare the electron conduction nanostructure by the method that is known in the art.For example, TiO 2Nanotube can be made by the titanium metal film that anodic oxidation (anodize) titanium metal film or anodic oxidation are deposited on the tin oxide that fluorine mixes.The electrical-conductive nanometer structure also can prepare by adopting the glue growth (colloidal growth) that is promoted by the seed grain that is deposited on substrate (seed particle).The electrical-conductive nanometer structure also can prepare by waiting such as the vacuum deposition process of chemical vapor deposition (CVD) and metal organic chemical vapor deposition (MOCVD), such as the epitaxial growth method of molecular beam epitaxy (MBE).
Under the situation of nanotube, the overall diameter scope of nanotube be from about 20 nanometers to 100 nanometers, be in some cases from 20 nanometers to 50 nanometers and in other cases for from 50 nanometers to 100 nanometers.The interior diameter of nanotube can be from about 10 nanometers to 80 nanometers, in some cases from 20 nanometers to 80 nanometers, in other cases from 60 nanometers to 80 nanometers.The wall thickness of nanotube can be 10-25 nanometer, 15-25 nanometer or 20-25 nanometer.In some cases, the length of nanotube is 100-800 nanometer, 400-800 nanometer or 200-400 nanometer.
Under the situation of nano wire, diameter can and can have the 50-100 micron long from about 100 nanometers to about 200 nanometers.Nanometer rods can have from the diameter of about 2-200 nanometer but usually diameter is 5-100 nanometer or 20-50 nanometer.Their length can be the 20-100 nanometer, but usually length is between 50-500 nanometer or 20-50 nanometer.
As used herein, term " nano particle " or " photosensitive nanoparticles " expression produces the light-sensitive material of electron hole pair when being exposed to solar radiation.Photosensitive nanoparticles is nanocrystal normally, for example quantum dot, nanometer rods, nanometer bipod (nanobipod), nanometer tribrach (nanotripod), nanometer multiway platform (nanomultipod) or nano wire.
Photosensitive nanoparticles can be made by the compound semiconductor that comprises II-VI, II-IV and III-V family material.Some examples of photosensitive nanoparticles are CdSe, ZnSe, PbSe, InP, PbS, ZnS, CdTe, Si, Ge, SiGe, CdHgTe or II-VI, II-IV and III-V family material.Photosensitive nanoparticles can be caryogram or nuclear-shell (core-shell) type.In core-shell nanoparticles, nuclear and shell are made from a variety of materials.Nuclear and shell can be made by compound semiconductor.
Quantum dot is preferred nano particle.Just as known in the art, has same composition but quantum dot with different-diameter absorbs and emitted radiation at different wave length.Fig. 1 illustrates and is made by same composition but have three kinds of quantum dots of different-diameter.Little quantum dot absorbs and emission at the blue portion of spectrum; And medium and big the quantum dot green in visible spectrum and redness respectively partially absorb and launch.Alternatively, as shown in Figure 2, quantum dot can be for essentially identical size but is made from a variety of materials.For example, the quantum dot of UV absorption can be made by zinc selenide (zinc selenide); And visible and IR quantum dot can be made by cadmium selenide (cadmium selenide) and lead selenide (lead selenide) respectively.Having the nano particle of different size and/or component can be randomly or use in layer to be manufactured on (1) UV and as seen; (2) solar cell in the broadband of visible and IR or (3) UV, visible and IR absorption.
Photoactive nanoparticle can be modified to comprise bridging agent (linker) X a-R n-Y bWherein X and Y can be the reactive group (reactive moiety) such as carboxylic acid group (carboxylic acid group), phosphate (phosphonic acid group), sulfonic group (sulfonic acid group) or amino-contained etc., a and b are 0 or 1 independently, wherein at least one is 1 among a and the b, and R is such as-CH 2,-NH-or-the containing carbon back, nitrogenous base or contain the oxygen base of O-, n is 0-10 or 0-5.One reactive group can another reactive group can react with nanostructure with the nano particle reaction.For example, when being deposited on two layers of nanoparticles on the nanostructure, the nano particle of basic unit can contain have can with the bridging agent of the acidic functionality (acid functionality) of metal oxide nanostructure Cheng Jian.The elementary cell that the nano particle of the second layer can contain such as amido or hydroxyl (hydroyl group) forms amido link (amide bond) or ester bond (ester bond) with the acidic group with the first nano particle bridging agent.Bridging agent is also with the nano particle passivation and increase their stability, photo absorption performance and photoluminescence performance.They also can improve dissolubility (solubility) or the suspension (suspension) of nano particle in ordinary organic solvents.
On the nano particle of functionalization and the nanostructure such as the suitable reactive group reaction of hydroxyl or other with individual layer by molecule self-assembly process (molecular self assembly process) deposition compact and continuous nano particle.By adjusting X a-R n-Y bComponent, the distance between the surface of (1) nanostructure and nano particle or (2) nano particle and another nano particle can be adjusted to the effect of the surface state that promotes charge recombination is minimized.Distance between these surfaces typically is 10 dusts or littler, is preferably 5 dusts or littler.Keep this distance to make the nanostructure tunnelling of electronics from the nano particle to the highly conductive by this gap.This easy electric transmission helps to reduce charge recombination and cause effective separation of charge, and this will cause effective solar energy converting.
As used herein, " hole transmission layer " is the electrolyte (electrolyte) of preferential conduction hole.Hole transmission layer can be the inorganic molecule that (1) comprises the semi-conducting material that the p such as the silicon of p type amorphous or crystallite or germanium mixes, (2) such as the organic molecule of metal-phthalein cyanogen compound (metal-thalocyanine), arylamine (arylamine) etc., and (3) for example poly-ethylidene dioxy thiophene (polyethylenethioxythiophene, PEDOT), the conducting polymer of P3HT, P3OT and MEH-PPV.
Shown in Figure 6 is the first transparent electrode and the solar cell of the second electrode combination with aforementioned nanostructure, nano particle and hole transmission layer and at least one to solar radiation.Make this solar cell also as in 5F, listing according to the scheme (protocol) of example 1 at Fig. 5 A.
It should be understood that the ground floor that contains the electron conduction nanostructure preferably is not a pantostrat.But in some cases, this layer made by nanostructure at interval.So just, allow photosensitive nanoparticles is incorporated between the nanostructure.In this embodiment, the distance between the nanostructure considers that the size of nano particle also considers the number of the layer of the nano particle that will be applied to nanostructure.
Hypothetical nanoparticle is arranged on the nanostructure, and photoactive layer does not need to be uniform layer and since it can meet nanostructured layers three-dimensional structure all or part of and can be for continuous or discontinuous.
Similarly, hole transmission layer has the structure on the surface that meets shape that is positioned at the solar cell layer under it and the electrode that electrically contacts with it.In certain embodiments, hole transmission layer contacts with second electrode with photosensitive nanoparticles.
In a preferred embodiment, the barrier layer is arranged between the whole conductive layer and first electrode.This layer can be made during nanostructure forms simultaneously, for example, works as TiO 2When making, makes nanotube this layer on titanium foil.
In certain embodiments, solar cell is the broadband solar cell that can absorb the solar radiation of different wave length.When the light time that is exposed to specific wavelength, photosensitive nanoparticles produces electron-hole pair.The band gap of photosensitive nanoparticles can be adjusted by the particle size or the component that change nano particle.By the nano material combination that is used to make nano particle, can realize wide band absorption to part or whole solar spectrum with the nanoparticle size and the certain limit of certain limit.Therefore, in one embodiment, have the mixture of the photosensitive nanoparticles of different size and/or component can be on the nanostructure of ground floor stratification to make the broadband solar devices of listing such as Figure 11 to 13.
Alternatively, the nano particle of different size and/or component can form the multilayer of the different piece of every layer of response solar spectrum separately.Can in Figure 14-17, find the example of such solar cell.In such embodiments, preferably nano particle is made the longer radiation of the wavelength that material absorbed of the layer absorptance formation second layer of close nanostructure by layering.If there be the 3rd layer, preferably the second layer is than the 3rd layer of longer wavelength absorption of the wavelength that is absorbed, or the like.
Example 1
Nanoparticle sensitized solar cell shown in Figure 6.The essential committed step of the solar cell shown in the shop drawings 6 is shown in Fig. 5 A-5F.By adopting method as known in the art, suitable transparency carrier (510) at first applies the stannic oxide layer (520) that fluorine mixes, and then deposits the ti thin film layer (530) of 300nm to 2 micron thickness by magnetron sputtering (magnetron sputtering) or other thin film deposition processes.By adopting method as known in the art, Ti film (530) by anodic oxidation and heat treated to obtain transparent TiO 2Nanotube (540).Anodic oxidation condition is optimised the barrier layer (550) that is similar to insulator and prevents the short circuit of cathode/anode in the solar cell to obtain acting on.TiO 2Nanotube surface contains hydroxyl (OH) functional group (560).Have the appropriate functional base (COOH ,-NH 2,-PO 4Perhaps-SO 3H) by the nano particle and the TiO that make such as the luminescent material of CdSe, ZnSe, PbSe, InP, PbS, III-V material 2The nanotube reaction is to obtain the TiO of nano particle (570) sensitization 2Nanotube.Shown in Fig. 5 D, nano particle comes the decorated nanometer pipe by forming individual layer by the molecule self-assembly process.Use solvent clean to remove the nano particle of loosel bound.Because nano particle is at TiO 2Deposition on the nanotube is by TiO 2On-OH functional group and nano particle functional group (COOH ,-NH 2,-PO 4,-SO 3H) reaction is controlled, so the thickness of nano particle automatically is restricted to several individual layers.Then, deposition hole transmission layer (580).Hole transmission layer can be for such as conducting polymer (for example: polymeric material PEDOT).Final electrode (transparent or semitransparent) (590) is deposited to finish battery.If translucent electrode (590) is deposited, battery can be oriented and make sunlight (100) drop on the transparency carrier (510) among Fig. 6 so then.When sunlight dropped on the solar cell shown in Fig. 6, electron hole pair was produced by nano particle.These nano particles can have various sizes, geometry and component to cover whole solar spectrum.Because luminous nano particle directly is attached to electron conduction TiO 2Nanotube is so thereby separation of charge takes place to be easy to minimizes any charge recombination.The solar cell of expectation shown in Fig. 6 have high efficiency and can with respect to other film and the low cost of silicon-based technologies under make.
Example 2
Another embodiment of nanoparticle sensitized solar cell shown in Figure 7.The essential committed step of making solar cell is similar to Fig. 5 A to shown in the 5F, except following.By adopting method as known in the art, titanium metal foil (710) by anodic oxidation to obtain transparent TiO 2Nanotube (730).The anodised condition of optimization is to obtain acting on the barrier layer (barrier layer) (720) that is similar to insulator and prevents the short circuit of cathode/anode in the solar cell.TiO 2Hydroxyl (OH) functional group is contained on the surface of nanotube (730).Have the appropriate functional base (COOH ,-NH 2,-H 2PO 4Perhaps-SO 3H) by the nano particle and the TiO that make such as the luminescent material of CdSe, ZnSe, PbSe, InP, PbS, III-V family material 2The nanotube reaction is to obtain the TiO of nano particle (750) sensitization 2Nanotube.Then, deposition hole transmission layer (760).Hole transmission layer can be the polymeric material such as conducting polymer, for example PEDOT.The conductive oxide layer (770) of last deposit transparent is to finish battery.Solar cell is oriented and makes sunlight (780) drop on the transparent conductive oxide layer (770).Expect solar cell shown in Figure 7 have high efficiency and can with respect to other film and the low cost of silicon-based technologies under make.
Example 3
Another embodiment of nanoparticle sensitized solar cell has been shown among Fig. 8.By adopting method as known in the art, suitable transparency carrier (810) at first applies the stannic oxide layer (820) that fluorine mixes, and then deposits the ti thin film layer of 300nm to 2 micron thickness by magnetron sputtering or other thin film deposition processes.By adopting method as known in the art, the Ti film by anodic oxidation and heat treated to obtain transparent TiO 2Nanometer rods (840).Anodised condition is optimised the barrier layer (850) that is similar to insulator and prevents the short circuit of cathode/anode in the solar cell to obtain acting on.TiO 2Nanorod surfaces contains hydroxyl (OH) functional group.Have the appropriate functional base (COOH ,-NH 2,-H 2PO 4Perhaps-SO 3H) by the nano particle and the TiO that make such as the luminescent material of CdSe, ZnSe, PbSe, InP, PbS, III-V material 2The nanometer rods reaction is to obtain the TiO of nano particle (870) sensitization 2Nanometer rods.Nano particle comes the decorated nanometer rod by forming individual layer by the molecule self-assembly process.Use solvent clean to remove the nano particle of loosel bound.Because nano particle is at TiO 2Deposition on the nanometer rods is by TiO 2On-OH functional group and nano particle functional group (COOH ,-NH 2,-PO 4,-SO 3H) reaction is controlled, so the thickness of nano particle automatically is restricted to the thickness of several individual layers.Hole transmission layer (880) is deposited then.Hole transmission layer can be the polymeric material such as conducting polymer, for example PEDOT.Last depositing electrode (transparent or translucent) (890) is to finish battery.If translucent electrode (890) is deposited, battery can be oriented and make sunlight (100) drop on the transparency carrier (810) so then.When sunlight dropped on the solar cell shown in Fig. 8, electron hole pair was produced by nano particle.Because nano particle directly is attached to electron conduction TiO 2So nanometer rods is compound thereby produce easy separation of charge minimum charge.
Example 4
Another embodiment of nanoparticle sensitized solar cell has been shown among Fig. 9.By adopting method as known in the art, Ti metal forming (910) by anodic oxidation to obtain transparent TiO 2Nanometer rods (930).Anodised condition is optimised and is similar to insulator and barrier layer (920) that prevent the short circuit of cathode/anode in the solar cell to obtain acting on.TiO 2Hydroxyl (OH) functional group is contained on nanometer rods (930) surface.Have the appropriate functional base (COOH ,-NH 2,-H 2PO 4Perhaps-SO 3H) by the nano particle and the TiO that make such as the luminescent material of CdSe, ZnSe, PbSe, InP, PbS, III-V family material 2The nanometer rods reaction is to obtain the TiO of nano particle (950) sensitization 2Nanometer rods.Nano particle comes the decorated nanometer rod by forming individual layer by the molecule self-assembly process.Use solvent clean to remove the nano particle of loosel bound.Because nano particle is at TiO 2Deposition on the nanometer rods is by TiO 2On-OH functional group and nano particle functional group (COOH ,-NH 2,-PO 4,-SO 3H) reaction is controlled, so the thickness of nano particle automatically is restricted to the thickness of several individual layers.Hole transmission layer (960) is deposited then.Hole transmission layer can be the polymeric material such as conducting polymer, for example PEDOT.Transparent conductive layer (970) such as ITO is deposited to finish battery at last.Solar cell is oriented and makes sunlight (980) drop on the transparent conductive layer (970).When sunlight dropped on the solar cell shown in Fig. 9, electron hole pair was produced by luminous nano particle.Because nano particle directly is attached to electron conduction TiO 2Nanometer rods is so thereby producing easy separation of charge minimizes charge recombination.
Example 5
In an alternative embodiment of the solar cell of Fig. 6, adopt the method for example 1, except following.At TiO 2After nanotube forms, have the nano particle and the TiO that make by Si, Ge or SiGe of suitable functional group 2The nanotube reaction is to obtain the TiO of nano particle (570) sensitization 2Nanotube.As shown in Figure 6, Si, Ge or SiGe nano particle (570) come the decorated nanometer pipe by forming individual layer by the molecule self-assembly process.
Hole transmission layer (580) is deposited then.Hole transmission layer can be the Si or the Ge of p doping.When using the Si nano particle, the Si that expectation uses p to mix.Silicon layer can be amorphous silicon or polysilicon.Hole transmission layer can deposit by the method as known in the art that employing is used to prepare the film of Si or Ge.Expectation realization and hole transmission layer be the coating nanometer particle conformally.This can realize by utilizing atom layer deposition process or chemical vapor deposition method deposition Si or Ge film.Si and Ge film can be deposited on the top of each other to increase the absorption to light.Under these circumstances, the effect of light-absorption layer is also played in the effect of not only playing hole transmission layer of Si and Ge film.Hole transmission layer also can be organic semiconductor or conductive polymeric material.
Another version of present embodiment be to the modification of the structure among Fig. 6,7,8 and 9 with the Si that utilizes Si, Ge or SiGe nano particle and/or p and mix and/or Ge as hole transmission layer.
Example 6
Have the TiO that is attached on the tin oxide that is based upon the fluorine doping 2The embodiment of the broadband solar cell of the nano silicon particles of many sizes of nanotube is shown in Figure 10.If follow the scheme of example 1, then by adopting method as known in the art, suitable transparency carrier (1010) is deposited.But, have the nano particle and the TiO of the different size of making by Si (1050), Ge (1060) or SiGe (1070) of suitable functional group 2Nanotube (1040) reacts the TiO with the broadband mixture sensitization that obtains nano particle 2Nanotube.As shown in figure 10, the nano particle of different size and/or component (1050,1060 and 1070) comes the decorated nanometer pipe by forming individual layer by the molecule self-assembly process.
Then, deposition hole transmission layer (1080).Hole transmission layer can be the Si or the Ge of p doping.When using the Si nano particle, the Si that expectation uses p to mix.Silicon layer can be amorphous silicon or polysilicon.Hole transmission layer can deposit by the method as known in the art that employing is used to prepare the film of Si or Ge.Si and Ge film can be deposited on the top of each other to increase the absorption to light.In the case, the effect of light-absorption layer is also played in the effect of not only playing hole transmission layer of Si and Ge film.Hole transmission layer also can be organic semiconductor or conductive polymeric material.
Another version of present embodiment is shown in Figure 11.In the case, transparent conductive oxide (TCO) layer (1190) is deposited on the top of hole transmission layer (1180) and solar cell and is oriented and makes sunlight drop on the TCO.Have the TiO on the tin oxide that fluorine mixes 2Another version of the present embodiment of nanometer rods (or nano wire) is shown in Figure 12.Have the TiO that is based upon on the titanium foil 2Another version of embodiment shown in Figure 13.Nanometer rods can be by comprising the method growth as known in the art of colloidal growth, chemical vapour deposition (CVD) and MBE.
Example 7
Have the TiO on the tin oxide that is based upon the fluorine doping 2The embodiment of the solar cell device of the nano silicon particles layer of the different size of nanotube higher slice is shown in Figure 14.Follow the scheme of example 1, except following.At TiO 2After nanotube (1440) formed, the nano particle of being made by Si, Ge or SiGe that has suitable functional group adopted the molecule self-assembly process to be deposited over TiO 2On the nanotube to obtain the TiO of multi-layer nano particle (1450,1460 and 1470) sensitization 2Nanotube.As shown in figure 14, by forming the nano particle of multilayer, nano particle (1450,1460 and 1470) comes the decorated nanometer pipe.Every layer in these layers is all adopted the molecule self-assembly process to deposit individually.Every layer of nano particle that can contain the narrow size range of making by Si or Ge.Every layer can be designed as the solar spectrum that absorbs narrow range.The expectation part (or all) of stacked by this way multilayer (1450,1460 and 1470) to cover solar spectrum.The number range of layer can from 2 to 10.Expectation number of layers minimum is to reduce manufacturing cost.By the scope of the particle size of use in being adjusted at every layer, can design the solar cell of number with preferred layer.Example shown in Figure 14 has three layers, and layer 1 (1450) absorbs in the IR scope, and layer 2 (1460) absorbs at visible-range, and layer 3 (1470) absorbs near ultraviolet (near UV) scope.The Si of various sizes and the combination in this embodiment of the nano particle of Ge.
Then, deposition hole transmission layer (1480).Hole transmission layer can be the Si or the Ge of p doping.When using the Si nano particle, the Si that expectation uses p to mix.Silicon layer can be amorphous silicon or polysilicon.Hole transmission layer can adopt the method as known in the art that is used to prepare Si or Ge film to deposit.Hole transmission layer also can be organic semiconductor or conductive polymeric material.
Other versions of this embodiment are shown in Figure 15,16 and 17.In Figure 15 and 17, transparent conductive oxide (TCO) layer (1590 or 1790) is deposited over the top of hole transmission layer (1580 or 1780) and solar cell and is oriented and makes sunlight drop on the TCO.
Has the TiO on the tin oxide that fluorine mixes 2Another version of this embodiment of nanometer rods (or nano wire) is shown in Figure 16.
Has the TiO that is based upon on the titanium foil 2Another version of the embodiment of nanometer rods (or nano wire) is shown in Figure 15.Nanometer rods can be by comprising the method growth as known in the art of colloidal growth, chemical vapour deposition (CVD) and MBE.
Example 8
In another embodiment, the scheme modifying of example 1 is as follows.At TiO 2After nanotube forms, have the photosensitive nanoparticles and the TiO that make by II-V, II-VI, II-IV family of suitable functional group 2The nanotube reaction is to obtain the TiO of nano particle (590) sensitization 2Nanotube.The example of these nano particles of (see figure 6) comprises CdSe, CdTe, ZnSe, PbSe, ZnS, PbS.As shown in Figure 6, nano particle comes the decorated nanometer pipe by forming individual layer by the molecule self-assembly process.
Hole transmission layer (580) is deposited then.Hole transmission layer can be the p doping semiconductor layer such as Si or Ge.Si or Ge layer can be amorphous or polycrystalline.Hole transmission layer also can be the metal oxide layer such as aluminium oxide, nickel oxide etc.Hole transmission layer can deposit by the method as known in the art that employing is used to deposit the film of these materials.For example, can deposit Si or Ge film by ald or chemical vapour deposition (CVD).Si and Ge film can be deposited on the top of each other to increase the absorption to light.In the case, the effect of light-absorption layer is also played in the effect of not only playing hole transmission layer of Si and Ge film.The thickness of hole transmission layer can be adjusted so that the resistance of the hole-conductive by this layer is minimum and make the absorption maximization of light.Hole transmission layer also can be organic semiconductor or conductive polymeric material.
Has the TiO that is based upon on the titanium foil 2Another version of the embodiment of nanotube is shown in Figure 7.In the case, transparent conductive oxide (TCO) layer (770) is deposited on the top of hole transmission layer (760) and solar cell and is oriented and makes sunlight drop on the TCO.Has the TiO on the tin oxide that fluorine mixes 2Another version of the embodiment of nanometer rods (or nano wire) is shown in Figure 8.Has the TiO that is based upon on the titanium foil 2Another version of the embodiment of nanometer rods (or nano wire) is shown in Figure 9.Nanometer rods can be by comprising the method growth as known in the art of colloidal growth, chemical vapour deposition (CVD) and molecular beam epitaxy (MBE).
Example 9
In another embodiment, the following modification of the scheme of example 8.The semiconductor layer such as Si or Ge that hole transmission layer is mixed by p makes to substitute the hole transmission layer of Si or Ge.
Other versions of this embodiment are shown in Figure 11,12 and 13.
Example 10
In another embodiment, the broadband solar cell of describing in example 6 is amended as follows.At TiO 2Nanotube (1440) forms back (seeing Figure 14), has the photosensitive nanoparticles and the TiO of the different size of being made by II-V, II-VI and II-IV family etc. of suitable functional group 2Nanotube reacts the TiO with the broadband mixture sensitization that obtains nano particle (1450,1460 and 1470) 2Nanotube.The example of photosensitive nanoparticles comprises CdSe, ZnSe, PbSe, CdTe, PbS etc.The size of nano particle can change in the 2-50nm scope, preferably from 2-10nm.The photosensitive nanoparticles that has the appropriate functional base uses the molecule self-assembly process to be deposited on TiO 2On the nanotube to obtain the TiO of multi-layer nano particle sensitization 2Nanotube.Every layer of these layers can deposit individually by adopting the molecule self-assembly process.Every layer of solar spectrum that can contain the photosensitive nanoparticles of narrow size range and can be designed to absorb narrow range.Multilayer (1450,1460 and 1470) thus the expectation part of stacked in this way covering solar spectrum (or all).The scope of the number of layer can from 2 to 10.Expectation minimum number target zone is to reduce manufacturing cost.By the size range of the particle of use in being adjusted at every layer, can design the solar cell of layer with preferred number.In Figure 14, layer 1 (1450) absorbs in the IR scope, and layer 2 (1460) absorbs in visible range, and layer 3 (1470) absorbs in the near ultraviolet scope.The nano particle of the PbSe of various sizes, CdSe and ZnSe can be in conjunction with to construct sandwich construction shown in Figure 14.
Hole transmission layer (1480) is deposited then.Hole transmission layer can be the semiconductor layer such as Si or Ge of p doping.This layer can be amorphous or polycrystalline.Si and Ge film can be deposited on the top of each other to increase the absorption to light.The effect of light-absorption layer is also played in the effect that Si and Ge film not only play hole transmission layer.The thickness of hole transmission layer can be adjusted so that the resistance of hole-conductive by this layer minimizes simultaneously that light absorption is maximized.Hole transmission layer also can be organic semiconductor or conductive polymeric material.
Other versions of present embodiment are shown in Figure 15,16 and 17.

Claims (30)

1. photovoltaic device, it comprises:
First electrode and second electrode, at least one is transparent to solar radiation in described two electrodes;
Ground floor, it comprises electron conduction nanostructure and logical with described first electrode conductance;
Photoactive layer, it comprises photosensitive nanoparticles and contiguous described electron conduction nanostructure; And
Hole transmission layer, it contacts described photoactive layer and described second electrode.
2. photovoltaic device as claimed in claim 1 also is included in the barrier layer between described hole transmission layer and described first electrode.
3. photovoltaic device as claimed in claim 1, wherein said electron conduction nanostructure comprises nanotube, nanometer rods or nano wire.
4. photovoltaic device as claimed in claim 3, wherein said nanostructure comprises nanotube.
5. photovoltaic device as claimed in claim 4, wherein said nanotube comprises titanium dioxide.
6. photovoltaic device as claimed in claim 1, wherein said photosensitive nanoparticles comprise quantum dot, nanometer rods, nanometer bipod, nanometer tribrach, nanometer multiway platform or nano wire.
7. photovoltaic device as claimed in claim 6, wherein said photosensitive nanoparticles is a quantum dot.
8. photovoltaic device as claimed in claim 1, wherein said photosensitive nanoparticles is covalently attached to described nanostructure.
9. photovoltaic device as claimed in claim 1, wherein said photosensitive nanoparticles comprise CdSe, ZnSe, PbSe, InP, PbS, ZnS, Si, Ge, SiGe, CdTe, CdHgTe or II-VI, II-IV or III-V family material.
10. photovoltaic device as claimed in claim 1, wherein said photoactive layer comprise first nano particle and second nano particle of absorption from the radiation of solar spectrum different piece.
11. photovoltaic device as claimed in claim 10, wherein said first nano particle is different on component with second nano particle.
12. photovoltaic device as claimed in claim 10, wherein said first nano particle and second nano particle are of different sizes.
13. photovoltaic device as claimed in claim 10, wherein said first nano particle and second nano particle are different on size and component.
14. photovoltaic device as claimed in claim 1 also comprises second photoactive layer, the wherein said ground floor and the described second layer absorb the radiation from the different piece of solar spectrum.
15. photovoltaic device as claimed in claim 14, the described nano particle of wherein said first photoactive layer and described second photoactive layer is different on component.
16. photovoltaic device as claimed in claim 14, the described nano particle of wherein said first photoactive layer and described second photoactive layer is of different sizes.
17. photovoltaic device as claimed in claim 14, the described nano particle of wherein said first photoactive layer and described second photoactive layer is different on size and component.
18. photovoltaic device as claimed in claim 1, wherein said hole transmission layer comprises hole transport polymer.
19. photovoltaic device as claimed in claim 18, wherein said hole transport polymer comprise p N-type semiconductor N polymer.
20. photovoltaic device as claimed in claim 19, wherein said p N-type semiconductor N polymer comprises P3HT, P3OT, MEH-PPV or PEDOT.
21. photovoltaic device as claimed in claim 20, wherein said polymer comprises PEDOT.
22. photovoltaic device as claimed in claim 1, wherein said hole transmission layer comprises the p N-type semiconductor N.
The SiGe that Ge that Si, p that 23. photovoltaic device as claimed in claim 22, wherein said p N-type semiconductor N are p to mix mix or p mix.
24. photovoltaic device as claimed in claim 22, wherein said p N-type semiconductor N comprise the microcrystal silicon of p doped amorphous silicon, p doping or the nanocrystal silicon that p mixes.
25. photovoltaic device as claimed in claim 1, wherein said hole transmission layer comprise the p N-type semiconductor N of two-layer or multilayer.
26. photovoltaic device as claimed in claim 25, wherein said p type semiconductor layer comprise silicon layer, the germanium layer of p doping or the SiGe layer that p mixes that p mixes.
27. a method that is used to make photovoltaic device comprises:
Form the ground floor that comprises the electron conduction nanostructure on first electrode, wherein said ground floor and described first electrode conductance are logical;
On described electron conduction nanostructure, form the photoactive layer that comprises photosensitive nanoparticles; With
On described photoactive layer, form hole transmission layer; And
On described hole transmission layer, form described second electrode;
In wherein said first electrode and described second electrode at least one is transparent to solar radiation.
28. method as claimed in claim 27 forms the barrier layer before also being included in the described nanostructure of formation or forming described hole transmission layer.
29. method as claimed in claim 27, the described formation of wherein said photoactive layer comprise the photoactive layer that uses different nano particles to comprise the random distribution of described different nano particle with manufacturing.
30. method as claimed in claim 27, the described method that wherein said photoactive layer comprises two-layer at least different nano particle and forms described photoactive layer is included in layer that forms first nano particle on the described nanostructure and the layer that forms second nano particle on the layer of described first nano particle, and wherein said first nano particle is different with second nano particle.
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