CN103107214A - Nanometer dipole solar cell and preparation method thereof - Google Patents
Nanometer dipole solar cell and preparation method thereof Download PDFInfo
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- CN103107214A CN103107214A CN2011103581351A CN201110358135A CN103107214A CN 103107214 A CN103107214 A CN 103107214A CN 2011103581351 A CN2011103581351 A CN 2011103581351A CN 201110358135 A CN201110358135 A CN 201110358135A CN 103107214 A CN103107214 A CN 103107214A
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Abstract
The invention provides a nanometer dipole solar cell and a preparation method thereof. A photovoltaic effect layer (116) is jointly formed by materials with photovoltaic effects and nanometer dipole particles embedded in the photovoltaic effect materials. The nanometer dipole particles have electric dipole moments or piezoelectric properties. The electric dipole moments of the nanometer dipole particles are polarized and at least parts of the electric dipole moments are arranged in the same direction. The direction of polarization of the nanometer dipole particles has weight in the direction perpendicular to a transparent electric conduction electrode layer or an electric conduction electrode layer, and the nanometer dipole particles provide a macroscopic electric field which is needed by separation of photoproduction charge. The photovoltaic effect layer can generate current and voltage when the photovoltaic effect layer receives electromagnetic wave radiation. Due to the fact that n-type mixed materials and p-type mixed materials are simultaneously deposited on a substrate, a needed solar cell is obtained.
Description
Technical field
The present invention relates to a kind of solar cell without the planar junction electric field and preparation method thereof.
Background technology
Solar cell adopts the semi-conducting material at smooth interface to collect incident light energy and generating usually.Semi-conducting material is divided into two classes usually: the electron rich material is N-shaped semi-conducting material and the p-type semiconductor that is rich in hole or depleted of electrons attitude.When solar cell is exposed to light source lower time, the electron motion in the N-shaped layer also passes the planar junction that semi-conducting material consists of and arrives the p-type layer and generation current.The generating capacity of solar cell is relevant with the surface area of p-n junction.Solar cell with single p-n junction may have larger surface area.Solar cell can adopt laminated construction to form many p-n junctions.In fact, multijunction solar cell is that the single junction cell to the specific band optical transparency is stacked up.These multijunction cells may produce the power output identical or larger with single p-n junction battery.
Figure 1A and Figure 1B have provided conventional p-n junction type solar cell 10.Solar cell 10 has substrate layer 12, is used for supporting transparent conductive oxide (TCO) layer 14.Solar cell 10 comprises p-type semiconductor layer 16, N-shaped semiconductor layer 18, and conventional plane p-n junction 20.As shown in the direction of arrow of Figure 1B, the preparation process of solar cell 10 is, deposition tco layer 14 is on substrate layer 12, and then N-shaped layer 18 (being made of cadmium sulfide (CdS)) deposits on tco layer 14.P-type layer 16 (being made of cadmium telluride (CdTe)) is deposited on N-shaped layer 18, and p-n junction 20 has planar structure by the direct formation that contacts of N-shaped layer 18 and p-type layer 16.Last metallic conduction electrode layer 22 deposits to the preparation of completing solar cell on p-type layer 16.As mentioned above, p-type layer 16 and N-shaped layer 18 prepare respectively and obtain from different targets.Thereby constructed p-n junction 20 is used for forming electronics from p-type layer 16 to N-shaped layer 18 with the transmission generating of hole from N-shaped layer 18 to p-type layer 16.
Yet the battery of every type has certain function limit.The unijunction photovoltaic cell may allow the light in broadband to reach p-n junction very much, yet is subject to selected materials, can not utilize all to reach the light of p-n junction.Many p-n junctions can utilize the light of specific band, but add up along with these are stacked, and every one deck can stop that all some are to the useful light of lower floor's generating.And each layer also to need be " currents match ", to guarantee the equal and opposite in direction of output current, because minimum output current is the factor of the total output of restriction battery.Currents match has the selectional restriction of material on the material of close output at those equally.Along with the increase of the number of plies, the resistance in battery will cause extra parasitic loss and reduce battery efficiency.And the step of preparation multijunction cell is complicated, has also increased the battery cost.Therefore, unijunction and multijunction solar cell meet each other half way to improve battery efficiency and power output always between battery size, flexibility, cost.
In prior art, the planar semiconductor layer preparation technology of solar cell is that sequential and per step is relatively independent.Every one deck can realize with different process, as, chemistry or physical vapour deposition (PVD) or sputter.Usually upward follow one deck under preparation at outermost metallic conduction electrode layer (as back electrode) or transparency conducting layer (as the front window layer).Be called as " lower substrate " when substrate is close to dorsum electrode layer, be called as " upper substrate " when substrate is close to the front window layer, depend on the relative order of each layer when using.
Usually, can form with different materials each semiconductor layer.For example, thin-film solar cells may have cadmium sulfide (CdS) N-shaped layer and cadmium telluride (CdTe) p-type layer.Can use different source materials grow in order these the layer.If sputter deposition craft, source material refers to target, by the high energy particle energetic ion of plasma (as contain) bombardment.The atom of material is shelled out from target and clashes into the battery layers surface that has prepared.Every one deck target used is all different.In single chamber by changing target or selecting different target as sputter can realize preparing each layer semiconductor required in battery.
Yet this preparation method can affect cost and the quality of solar cell.The deposition of every layer must be carried out in order, and deposition velocity is slow, causes throughput rate on the low side.If the use single chamber, changing target can increase technique and processing time and chamber is polluted.If at the different target of different chamber sputters, equipment and maintenance cost can increase according to process choice.In addition, single chamber prepared battery limitation the batch production solar cell output.If realize high production capacity with multi-chamber, i.e. pipeline system production will significantly increase equipment cost.Therefore, ideal situation is to produce all low and large solar cells of p-n junction surface area of a kind of surface area and thickness.
Compare with the photovoltaic device with p-n junction junction field structure, nanometer dipole photovoltaic device can have following basic advantage in theory: 1) can realize symmetrical structure, substrate is descending with impact does not have difference on battery efficiency in upper structure, be free to select transparent or opaque backing material, also be free to select rigidity or flexible backing material; 2) be expected to obtain higher output voltage; 3) only need one deck to be embedded with the material of nanometer dipole, rather than such two-layer of p-n junction, greatly reduce equipment cost (estimate approximately half) and the production technology of film preparation; 4) do not need good electrically contacting between nanometer dipole material and photovoltaic effect medium, therefore alternative photovoltaic medium and nanometer dipole particle type are many, are subjected to the restriction of raw material supply few.
Utilize the nanometer dipole preparation method of solar battery of this invention, can further promote conversion efficiency, uniformity and the yield rate of thin-film solar cells, have the height diversity.The preparation method of this nanometer dipole solar cell can produce on existing CdTe thin-film solar cells production line, can reduce expensive vacuum equipment cost.
The technology of dipole antenna array battery of the prior art is such as " Theory and Manufacturing Processes of Solar Nanoantenna Electromagnetic Collectors " literary composition of Journal of Solar Energy Engineering 132 curly hair tables February in 2010 is described.Its principle is that the dipoles scatter sub antenna by array arrangement produces alternating current to electromagnetic induction and produces absorption to solar energy, but the biggest problem that present this technology runs into is 10
13-10
16The high-frequency rectification diode of Hz (visible light wave range) does not also exist, and therefore this battery reality does not also realize.And dipole antenna array battery absorbs solar photon by dipole, and nanometer dipole antenna array battery is that with costlinesses such as the processing of electron beam micro-nano, X-ray lithographies and slowly technology is made, and cost of manufacture is very high.
The preparation method of solar cell needs two kinds of remarkable different compositions to form enough strong p-n junction electric field at least at present, requires simultaneously to keep between them excellent electric contact.This essential disadvantages of prior art has caused must depositing respectively in order by every layer material in producing the solar cell process.If at single vacuum chamber deposition different materials, may produce cross pollution, and limit the speed of production of solar cell.If according at the different target of different chamber sputters, equipment and maintenance cost can increase.
Summary of the invention
The objective of the invention is to overcome the above-mentioned shortcoming of prior art, propose a kind of solar cell and preparation method thereof, and the method for the macro property of the described solar cell of quantization signifying and its microstructure and polarization characteristic Relations Among.The surface area of solar cell of the present invention and thickness are all lower, and the p-n junction surface area ratio is larger.
The structure of solar cell of the present invention is:
Described solar cell comprises substrate layer, the first transparency conductive electrode layer, photovoltaic effect layer and the second conductive electrode layer, and wherein the second conductive electrode layer is made by transparent material or opaque material.The position relationship of described each layer with sunlight enter arranged sequentially, be followed successively by the first transparency conductive electrode layer, photovoltaic effect layer and the second conductive electrode layer.When substrate layer is when being made into by opaque material, as glass or transparent organopolysiloxane film, before substrate layer can be positioned at the first transparency conductive electrode layer; When substrate layer is made of opaque material, as thin aluminium foil, molybdenum foil, stainless steel substrates, after substrate layer must be positioned at the second conductive electrode layer.
Described photovoltaic effect layer is made of jointly the material with photovoltaic effect and the nanometer dipole particle that is embedded in the photovoltaic effect material, and described nanometer dipole particle has polarization or piezoelectric properties.
Be with the structural similarity part of traditional p-n junction battery or similar junction field battery, the present invention is made of photovoltaic effect layer and two conductive layers.Different from p-n junction battery or similar junction field battery is, the photovoltaic effect layer of battery of the present invention only has independent one deck, and traditional p-n junction battery needs p-type layer and N-shaped layer each one deck at least.And, the photovoltaic effect layer of nanometer dipole battery of the present invention be by the material with photovoltaic effect and wherein the nanometer dipole particle of patchiness jointly consist of, the electric dipole moment of described nanometer dipole particle (as nano particle) can form internal electric field when arranging in the same way; When the direction that electric dipole moment is arranged in the same way is important on the direction perpendicular to transparency conductive electrode layer or conductive electrode layer, will generation current and voltage under electromagnetic radiation; The first transparency conductive electrode layer allows photon to pass through, and produces photo-generated carrier after photon is absorbed by the photovoltaic effect layer; A kind of photo-generated carrier that is produced by the first transparency conductive electrode layer collection photovoltaics effect layer simultaneously, the second conductive electrode layer is collected another kind of photo-generated carrier; Substrate layer provides mechanical support for solar cell of the present invention.
Described the first transparency conductive electrode layer can allow the electromagnetic wave of certain wave band penetrate and have electrical conductance.Permeable electromagnetic radiation be a kind of wavelength less than the light of 1100nm, comprise near-infrared, visible light and ultraviolet light.
Described photovoltaic effect layer contacts with the first transparency conductive electrode layer, is used for absorbing a part by the electromagnetic wave of the first transparency conductive electrode layer.The photovoltaic effect layer includes nanometer dipole particle, and described nanometer dipole particle can be a kind of in p-type or N-shaped semi-conducting material, and the photovoltaic dielectric material is the another kind in p-type or N-shaped material.For example the present invention uses the CdS of N-shaped or the CdS of rich S
xTe
(1-x)The nano particle that alloy consists of, the photovoltaic medium is made of the CdTe photovoltaic dielectric material of p-type.From nano particle to the CdS-CdTe alloy transition district that has gradual change CdTe photovoltaic medium, alloy has higher S composition near near nanometer dipole particle, has higher Te composition near near CdTe photovoltaic medium.The transition region of CdS-CdTe alloy is described as CdS
xTe
(1-x)Wherein, what x characterized is the relative composition of sulphur and tellurium, and x=0 represents not sulfur-bearing, and x=1 represents not contain tellurium.Each the CdS nano particle that is embedded in the photovoltaic layer of dielectric material produces the electric dipole with electric dipole moment, and the formation electric field relevant to electric dipole.The formation of electric dipole is the ion because of a surface enrichment positively charged of nano particle, as cadmium Cd atom, at the relative electronegative ion of another side enrichment, as sulphur S atom.At least part of appearance of electric dipole is arranged relatively in the same way, and polarised direction is towards perpendicular to TCO or conductive electrode layer.One in TCO or conductive electrode layer usually of the Cd atom in the CdS electric dipole for example, and S atom another in TCO or conductive electrode layer usually.
Described the second conductive electrode layer can be and the first same or similar transparent conductive oxide of transparency conductive electrode layer (TCO) material, can be also opaque electric conducting material, as metal, graphite etc.Described the second conductive electrode layer is used for forming with the first transparency conductive electrode layer the positive and negative polarities of solar cell, can connect load, electric current and voltage that the output battery produces.
The preparation method of solar cell of the present invention is the mixture of deposition N-shaped material and p-type material on the backing material that has covered the transparency conductive electrode layer simultaneously, and a step is made the photovoltaic effect layer of solar cell.
Preparation method of solar battery of the present invention specifically describes as follows:
At first the mixed film for preparing N-shaped material and p-type material, then (Phase Segregation) characteristic that is separated by bi-material in high-temperature heat treatment process are isolated N-shaped material and p-type material.When the N-shaped material had dipolar nature, the method just can be formed on numerous molecules of inlaying the N-shaped material formation with dipole moment in the p-type material; When the p-type material has dipolar nature, just can form numerous molecules of inlaying the p-type material formation with dipole moment in the N-shaped material.
Take p-type CdTe photovoltaic effect material and N-shaped CdS piezoelectric as example, the present invention forms the molecule with electric dipole moment in photovoltaic film concrete preparation method is: use cadmium sulfide CdS and cadmium telluride CdTe bi-material to mix the target of compacting, described target is in CdS: the CdTe mass ratio is after the ratio between 1: 2.5 to 1: 30 is mixed, 1000 to 10000N/cm
2Pressure under compacting form target; Adopt the method for vacuum sputtering, have transparent conductive oxide (TCO) conductive layer, be i.e. deposition CdSTe alloy firm on the glass substrate of the second conductive electrode layer; And through heat treatment, heat-treatment temperature range is 350 ℃ to 650 ℃, is incubated 10-120 minute, makes the CdSTe alloy issue looks at specified temp and separates, and as shown in Figure 4, forms the molecule that is rich in CdS in the CdSTe film.
Described cadmium sulfide CdS is a kind of piezoelectric, its molecule has obvious electric dipole moment, in its forming process, can nature be arranged in roughly consistent, perpendicular to transparent conductive oxide (TCO) conductive layer, i.e. the direction on the first transparency conductive electrode layer surface.This roughly consistent internal electric field of arranging in the same way and having consisted of alternative p-n junction perpendicular to macroscopical electric field that the electric dipole of electrode layer forms.
Preparation method of the present invention is similar to traditional C dS/CdTe hull cell, uses vacuum deposition method, can directly realize in conventional equipment.But conventional method need to prepare at least double-layer films (being N-shaped CdS and p-type CdTe layer) and realize photovoltaic effect, and the present invention only need prepare one deck CdSTe film just can realize photovoltaic effect.
The present invention has utilized this semi-conducting material with piezoelectric properties of CdS.CdS is the same with other II-VI family material have significantly ionic.Its most stable crystal structure is wurtzite structure, belongs to hexagonal crystal system, does not have a mirror symmetry.Therefore, can form respectively positive elecrtonegativity due to the asymmetric CdS of the making crystal of the distribution of Cd and S ion on relative two sides and with electric dipole moment.The CdS particle of nano-scale with dipole moment, roughly arrange in the same way under electric field force outside, and still keep certain electric polarity after eliminate in the outfield, be i.e. so-called ferroelectric effect.
The present invention prepares one of preparation method of described nanometer dipole solar cell and comprises following steps:
A) cleaning is coated with the glass substrate of described the first transparency conductive electrode layer, then the mixed film of sputtering sedimentation CdTe and CdS on described glass substrate, described film thickness scope is 0.2-20 μ m, the target that uses as CdS and CdTe in mass ratio 1: 30-1: compacting after 2.5 scopes are mixed;
The glass substrate that b) will deposit CdTe and CdS mixed film is placed in CdCl
2With heat treatment in the mixed-gas atmosphere of air, heating-up temperature is 350～650 ℃, temperature retention time 5-120 minute;
C) at CdCl
2Film surface after heat treatment re-uses described the second conductive electrode layer of sputtering method deposition, forms described solar cell.
Implementing described step mistake! Do not find Reference source.With step b) time, applying polarized electric field on described the first transparency conductive electrode layer, voltage is 10～3000V, and the CdTe and the CdS mixed film that deposit are placed among electric field.
The present invention prepare described nanometer dipole solar cell the preparation method two comprise following steps:
A) cleaning is coated with the glass substrate of described the second conductive electrode layer, then sputtering sedimentation CdTe and CdS mixed film on described glass substrate, described film thickness scope is 0.2-20 μ m, and the target that uses presses 1 as CdS and CdTe: 30-1: suppress after 2.5 (mass ratio) mixes;
The glass substrate that b) will deposit CdTe and CdS mixed film is placed in CdCl
2Heat treatment in the mist of steam and air, heat treatment temperature are 350～650 ℃, and temperature retention time is 5-120 minute;
C) at step b) CdCl
2Film surface after heat treatment deposits the first transparency conductive electrode layer again, forms complete solar cell.
Implementing described step mistake! Do not find Reference source.And b) time, apply polarized electric field on described the first transparency conductive electrode layer, voltage is 10～3000V, and the CdTe and the CdS mixed film that deposit are placed among electric field.
The present invention drives the nanometer dipole with dipole moment and arranges in the same way the method that forms macroscopical internal electric field and have two kinds:
1) be deposited on the first transparency conductive electrode layer or the second conductive electrode layer before heat treatment due to the CdSTe alloy firm, in heat treatment process, can utilize the image force effect of this two-layer conductive electrode layer, at the granuloplastic nanometer dipole particle that drives simultaneously of nanometer dipole along arranging in the same way perpendicular to the direction of described conductive electrode layer;
2) can deposit again one deck conductive electrode layer after the CdSTe alloy firm or cover non-contiguously layer of conductive material, apply the external dc biasing electric field of 10～3000V after the CdSTe alloy firm, drive the arrangement in the same way of nanometer dipole between described conductive electrode layer and this layer conductive electrode layer that deposits again or conductive material layer.Both can utilize the image force of TCO and the arrangement in the same way that extra electric field drives the nanometer dipole in CdSTe alloy firm deposition process, also can utilize the image force of TCO and the arrangement in the same way that extra electric field drives the nanometer dipole after CdSTe alloy firm deposition.The method that forms electric dipole macroscopic view internal electric field is versatile and flexible, can do necessary adjustment in conjunction with different apparatus and process, can realize same purpose.
The first transparency conductive electrode layer that the present invention uses can be the zinc oxide (ZnO:Al that mixes aluminium
2O
3Or AZO), tin indium oxide (ITO), mix the tin oxide (SnO of fluorine
2: F or FTO) etc., can use the method for sputter or chemical vapour deposition (CVD) (CVD) to make.The second conductive electrode layer can be both that transparent conductive oxide can be also opaque metal, graphite etc., and the conductive electrode layers such as metal, graphite can adopt the preparation of sputter or electric plating method.
The present invention also proposes a kind of method of verifying nanometer dipole particle solar cell of the present invention, and this method utilization is based on the piezoelectric effect of the piezoelectric forces microscopy checking nanometer dipole of piezoelectric forces microscope (PFM) principle.The innovation of this method is to set up between conversion efficiency with the piezoelectric property of nanometer dipole particle and nanometer dipole particle solar cell and contacts directly, for the process modification of solar cell of the present invention, improve the macro property effect microcosmic and direct foundation are provided.
The present invention is by macro property and its microstructure and the polarization characteristic Relations Among of piezoelectric forces microscope (Piezoresponse Force Microscopy) quantization signifying nano particle solar cell, can be by longitudinal piezoelectric effect (Vertical PFM) and the piezo-electric traverse effect (Lateral PFM) of scanning survey solar cell of the present invention, scan and seek evidence and the distributed intelligence that the nanometer dipole exists, obtain simultaneously the information of the local polarisation direction distribution of electric dipole by vectorial piezoelectric effect (Vector PFM) scanning.Under contact mode, film surface is applied a concussion voltage by the microscopical conducting probe of piezoelectric forces, can produce the deformation concussion of same frequency due to the piezoelectric property of electric dipole particle under the impact of this local biases, not have the other materials of piezoelectric property can not change.The position that coordinates piezoelectric forces microscope conducting probe, the distribution that just can draw out nanometer dipole particle.Nanometer dipole particle can cause the longitudinal oscillation of probe when flexible, produces longitudinal piezoelectric effect figure; Can cause the probe teeter during the tangential deformation of nanometer dipole particle, and produce piezo-electric traverse effect figure.The Oscillation Amplitude of nanometer dipole particle is directly proportional to polar intensity.And the polarised direction of nanometer dipole particle and applying bias field direction are when inconsistent, the phase place of deformation has and relatively lags behind, therefore this phase difference can provide the information of electric dipole polarised direction, and the information of electric dipole polarised direction is called vectorial piezoelectric effect figure.
Can obtain more detailed data by scanning film surface and cross section dual mode.Because the piezoelectric forces microscope is a kind of atomic force microscopy mirror system that conducting probe has been installed, resolution can reach nanometer scale, can directly also obtain accurately the information that the electric dipole polarized electric field distributes, this will be the direct verification method that proof CdS nanometer dipole exists in device.Make the information such as the size that can intuitively draw out in this way electric dipole particle in semiconductive thin film, distribution, local polarisation direction and intensity, for the optimization of nanometer dipole particle solar cell properties provides foundation.
Description of drawings
Figure 1A routine has the solar cell cross-sectional structure figure of plane p-n junction;
Figure 1B routine has preparation method's schematic diagram of plane p-n junction solar cell;
The solar battery structure schematic diagram of Fig. 2 A upper substrate of the present invention;
Solar battery structure schematic diagram during Fig. 2 B lower substrate of the present invention;
Preparation method's schematic diagram of Fig. 2 C solar cell of the present invention;
The cross section enlarged drawing of the nanometer dipole particle that Fig. 3 solar cell of the present invention is inlayed in the photovoltaic medium;
Fig. 4 relative component-part diagram of tellurium and sulphur under different temperatures in cadmium-tellurium-sulphur alloy, x is the relative amount of sulphur;
Fig. 5 A nanometer dipole particle enlarged drawing has marked S and Cd;
The film blank layer schematic diagram of the formation nano particle solar cell of Fig. 5 B the present invention preparation provided relatively chaotic electric dipole orientation in figure;
Fig. 5 C nano particle solar cell schematic diagram has provided relatively consistent electric dipole orientation in figure;
The another kind of nano particle solar battery structure of Fig. 5 D the present invention schematic diagram has provided the electric dipole orientation of high consistency in figure;
Incident electromagnetic wave wavelength and the external quantum efficiency graph of a relation of the different solar cells of Fig. 6;
Transformation efficiency and the CdCl of Fig. 7 A nano particle solar cell
2The box of processing time relation must be schemed;
Transformation efficiency and the CdCl of the planar junction battery of Fig. 7 B common process
2The box of processing time relation must be schemed;
Open circuit voltage and the CdCl of Fig. 8 A nano particle solar cell
2The box of processing time relation must be schemed;
Open circuit voltage and the CdCl of the planar junction battery of Fig. 8 B common process
2The box of processing time relation must be schemed;
Short circuit current and the CdCl of Fig. 9 A nano particle solar cell
2The box of processing time relation must be schemed;
Short circuit current and the CdCl of the planar junction battery of Fig. 9 B common process
2The box of processing time relation must be schemed;
The square value [(α * hv) of the absorption coefficient of the various films of Figure 10 and the product of corresponding energy hv
2] with the graph of a relation of band gap, compared the different of common process planar junction battery and nano particle solar cell;
Figure 11 uses the current-voltage curve of the CdS nanometer dipole solar cell that the present invention prepares;
Figure 12 A, Figure 12 B adopt the schematic diagram of piezoelectric forces microscope checking nanometer dipole solar cell.
Embodiment
Further illustrate the present invention below in conjunction with the drawings and the specific embodiments.
The structure of solar cell 100 of the present invention is as shown in Fig. 2 A, and the position relationship that forms described solar cell 100 each layers puts in order from inside to outside and is followed successively by: substrate layer 112, the first transparency conductive electrode layer 118, the photovoltaic effect layer 116 that contains nanometer dipole particle and the second conductive electrode layer 114.After substrate layer 112 also can be positioned at the second conductive electrode layer 114, other each layer invariant positions were as shown in Fig. 2 B.
Described substrate layer 112 is made of transparent material, and for example, glass, polyimides quasi-copolymer film can be also opaque metal levels, for example, and thin aluminium foil, molybdenum foil, stainless steel substrates.When substrate layer 112 is made of transparent material, first deposit the first transparency conductive electrode layer 118 on substrate layer 112, then priority depositing photovoltaic effect layer 116 and the second conductive electrode layer 114, as shown in Fig. 2 A.During use, electromagnetic wave as visible light, by transparent substrate layer 112 and the first transparency conductive electrode layer 118, enters photovoltaic effect layer 116.When substrate layer 112 is made of opaque material, need first the second conductive electrode layer 114 to be deposited on substrate layer 112, then priority depositing photovoltaic effect layer 116 and the first transparency conductive electrode layer 118, as shown in Fig. 2 B.And in use, electromagnetic wave needs to see through from the first transparency conductive electrode layer 118 and enters photovoltaic effect layer 116.
Described photovoltaic effect layer 116 is made of jointly the material with photovoltaic effect and the nanometer dipole particle that is embedded in the photovoltaic effect material, and described nanometer dipole particle has polarization or piezoelectric properties.
The first transparency conductive electrode layer 114 is transparent conductive oxides, as, the zinc oxide (ZnO:Al of alumina doped
2O
3Or AZO), tin indium oxide (ITO), mix the tin oxide (SnO of fluorine
2: F or FTO) etc.Therefore electromagnetic wave also can arrive adjacent lower one deck photovoltaic effect layer 116 by this layer.Adjacent lower one deck photovoltaic effect layer 116 can convert sunlight to electric energy.Described photovoltaic effect layer 116 is deposited between the first transparency conductive electrode layer 114 and the second conductive electrode layer 118.Photovoltaic effect layer 116 comprises p-type photovoltaic medium 122 and the N-shaped nano particle 120 that is included in wherein and is in contact with it.N-shaped nano particle 120 can partially or completely be embedded in p-type photovoltaic medium 122, as shown in Fig. 2 A.The N-shaped nano-particle material can be any semi-conducting material that can be used for preparing the N-shaped layer in the planar junction solar cell, for example, and CdS.
In the nano particle solar battery structure of another kind of form, the nano particle in the photovoltaic effect layer can be also p-type.The p-type nano particle can be partially or completely to be embedded in the photovoltaic dielectric material.The p-type nano particle can be any material that can be used for forming planar junction solar cell p-type layer.For example, the p-type nano particle can be ZnTe:N, or other material and material/doping combination.The ZnTe material can be in sputtering technology be realized doping to ZnTe by introducing nitrogen.Nitrogen is introduced in and forms ZnTe:N in the ZnTe material lattice as the p-type particle.
Figure 3 shows that photovoltaic effect layer 116 in Fig. 2 A amplification structure.Nano particle 120 represents with N-shaped CdS nano particle.P-type photovoltaic medium 122 is CdTe layers.Transition region 126 is present between N-shaped nano particle 120 and p-type photovoltaic medium 122.In a kind of non-limitative example of photovoltaic effect layer 116, transition region 126 is made of cadmium, sulphur and tellurium alloy.In a kind of version of nano particle solar cell 100, transition region 126 is characterized as being CdS
(x)Te
(1-x), wherein x represents CdS
(x)Te
(1-x)The relative composition of sulphur and tellurium in alloy, the span of x are that in scope between 0 to 1, x=0 represents not sulfur-bearing, and x=1 represents not contain tellurium.
Described transition region 126 is a kind of CdS
(x)Te
(1-x)Alloy is from rich tellurium zone to the gradual change in rich sulphur zone.Near the point of nano particle electric dipole CdS 120, x is 1.Along with distance increases to photovoltaic medium 122 gradually from nano particle 120 beginnings, the value of x gradually becomes 0.Therefore, along with moving to the photovoltaic medium, element T e replace gradually S and and the Cd combination.
In another kind of non-limitative example, x also can represent from the distance of the end to end of transition region 126, from photovoltaic medium 122 to nano particle 120.For example, at CdS
(x)Te
(1-x)In x can the linear distance 120 from photovoltaic medium 122 to nano particle in proportion to.
As shown in Fig. 2 C, in the method for preparing nano particle solar cell 100 of the present invention, by suitable depositing operation, as sputter, form the photovoltaic effect layer on the first transparency conductive electrode layer.
Sputter forms the first step of nanometer dipole particle solar cell 100 methods, and target 124 need be provided.The contained material of target 124 has suitable ingredients, in order to form the photovoltaic effect layer.Target 124 can be the mixture of alloy or metallic compound or simple substance, mixes as CdTe and CdS, or simple substance Cd, S and Te mixing.Target 124 can comprise any compound or element simple substance that is used for forming the photovoltaic effect layer, for example CdTe photovoltaic dielectric material and CdS.Target 124 can be by granulate mixture, and as the material that uses in powder metallurgical technique, or the compacting of the solid alloy material of required component forms.
The present invention prepares one of preparation method of described nanometer dipole solar cell and comprises following steps:
A) cleaning is coated with the glass substrate of described the first transparency conductive electrode layer, then the mixed film of sputtering sedimentation CdTe and CdS on described glass substrate, described film thickness scope is 0.2-20 μ m, the target that uses as CdS and CdTe in mass ratio 1: 30-1: compacting after 2.5 scopes are mixed;
The glass substrate that b) will deposit CdTe and CdS mixed film is placed in CdCl
2With in the mixed-gas atmosphere of air heat treatment 5-120 minute, heating-up temperature was 350～650 ℃;
C) at CdCl
2Film surface after heat treatment re-uses described the second conductive electrode layer of sputtering method deposition, forms described solar cell.
Implementing described step mistake! Do not find Reference source.And b) time, apply polarized electric field on described the first transparency conductive electrode layer, voltage is 10～3000V, and the CdTe and the CdS mixed film that deposit are placed among electric field.
The present invention prepare described nanometer dipole solar cell the preparation method two comprise following steps:
A) cleaning is coated with the glass substrate of described the second conductive electrode layer, then sputtering sedimentation CdTe and CdS mixed film on described glass substrate, described film thickness scope is 0.2-20 μ m, and the target that uses presses 1 as CdS and CdTe: 30-1: suppress after 2.5 (mass ratio) mixes;
The mixed film that b) will deposit CdTe and CdS is placed in CdCl
2Heat treatment in the mist of steam and air; Heat treatment temperature is 350～650 ℃, and temperature retention time is 5-120 minute;
C) at step b) CdCl
2Film surface after heat treatment deposits the first transparency conductive electrode layer again, forms complete solar cell.
Implementing described step mistake! Do not find Reference source.And b) time, apply polarized electric field on described the first transparency conductive electrode layer, voltage is 10～3000V, and the CdTe and the CdS mixed film that deposit are placed among electric field.
Below for preparing the embodiment of described solar cell.
At first high-purity ZnO:Al target of 99.999% is installed on the target position of magnetron sputtering apparatus; Then the glass substrate of cleaning is sent into the vacuum chamber of thermal evaporation apparatus, and be heated to 200 ℃; Vacuum chamber is evacuated to lower than 4 * 10
-4Pa; Be filled with argon gas in vacuum chamber to 2Pa; Open the radio frequency sputtering power supply, regulate this output power of power supply to 2.5W/cm
2, the distance between target and glass substrate is 10cm; The thick ZnO:Al transparent conductive film (TCO) of sputtering sedimentation 1.0 μ m, i.e. the first transparency conductive electrode layer under these process conditions.
Again with CdS and the CdTe ratio mixing of 1: 30 in mass ratio, at 6000N/cm
2Pressure under be pressed into the hybrid target material, this is mixed the target that target makes is installed on the target position of magnetron sputtering apparatus.The glass substrate that then will deposit the first transparency conductive electrode layer is sent in the vacuum chamber of magnetron sputtering apparatus, is heated to 250 ℃.Vacuum chamber is evacuated to lower than 4 * 10
-4Pa.Be filled with argon gas to 2Pa in vacuum chamber.Open the radio frequency sputtering power supply, regulate its power output to 2.5W/cm
2Distance between target and glass substrate is 10cm.The thick CdSTe alloy firm of sputtering sedimentation 02 μ m under these process conditions is made the solar battery thin film base layer structure that is made of substrate, the first transparency conductive electrode layer and photovoltaic effect layer, as 150 in Fig. 5 B.
As shown in Fig. 5 A, CdS electric dipole nano particle 200 is cadmium sulfide molecules of a polarization, has electric field 210 between positive pole 212 and negative pole 214.Can form N-shaped CdS nano particle 120 by one or more CdS electric dipole molecules 200.Have electric dipole moment between positive pole 212 and negative pole 214, its direction as shown by arrow A.Described solar battery thin film base layer 150 comprises many CdS nano particles 120.
Described solar battery thin film base layer structure 150 taken out from the sputter vacuum chamber.Fig. 5 C has provided electric dipole through CdCl
2Arrangement in the same way after heat treatment, wherein the electric dipole arrangement can be also rightabout, this depends on the cohesion forming process of nanometer dipole particle and the control of heating-up temperature.As shown in Fig. 5 C, nanometer dipole particle solar battery thin film base layer structure 150 is placed in CdCl
2In heat-treat by Technology for Heating Processing 160, namely containing CdCl
2Be heated to 350 ℃ in the mist of saturated steam and dry air, and be incubated 120 minutes, thus the nano particle solar cell 150 ' that forming section is arranged in the same way.CdS electric dipole 200 is at CdCl
2Reaction in treatment process 160 is to such an extent as to the electric dipole moment of each nano particle 120 is arranged with essentially identical direction.As shown in Fig. 5 C, the common direction of nano particle 120 is away from the first transparency conductive electrode layer 114.The in the same way arrangement of CdS electric dipole 200 in p-type photovoltaic medium 122 improved power stage and battery efficiency.Complete the CdCl as 160 or 170
2After heat treatment, cool to room temperature.
Then with CdCl
2Nanometer dipole particle solar battery thin film base layer structure after heat treatment sent into the vacuum chamber of this sputtering equipment, puts into 99.99% High Purity Gold in evaporator crucible; Vacuumize and reach lower than 4 * 10
-4Pa; Open heating power supply to the evaporator crucible power supply until gold dissolves; Open baffle plate to glass substrate hydatogenesis gold, thickness is 600nm, prepares the second conductive electrode layer, completes described solar cell preparation.
High-purity ZnO:Al target of 99.999% is installed on the target position of magnetron sputtering apparatus; Then the glass substrate of cleaning is sent into the vacuum chamber of thermal evaporation apparatus, and be heated to 200 ℃; Vacuum chamber is evacuated to lower than 4 * 10
-4Pa; Be filled with argon gas in vacuum chamber to 2Pa; Open the radio frequency sputtering power supply, regulate this output power of power supply to 2.5W/cm
2, the distance between target and glass substrate is 10cm; The thick ZnO:Al transparent conductive film (TCO) of sputtering sedimentation 1.0 μ m, i.e. the first transparency conductive electrode layer under these process conditions.
After the ratio of 1: 30 is mixed in mass ratio with ZnTe and CdTe, at 10000N/cm
2Pressure under be pressed into the hybrid target material, this is mixed the target that target is pressed into is installed on the target position of magnetron sputtering apparatus.Then the TCO Conducting Glass is sent in the vacuum chamber of this sputtering equipment, and be heated to 250 ℃; Vacuum chamber is evacuated to lower than 4 * 10
-4Pa; Be filled with argon Ar and nitrogen N in vacuum chamber
2Mist to 2Pa, the volume ratio of mist is Ar: N
2=97: 3; Open the radio frequency sputtering power supply, regulate the power output of this power supply to 2.5W/cm
2Distance between target and glass substrate is 10cm.The thick CdZnTe:N alloy firm of sputtering sedimentation 2.0 μ m under these process conditions is made nanometer dipole particle solar battery thin film base layer structure 150.
The TCO film of nanometer dipole particle solar battery thin film base layer structure 150 is added the direct voltage of 1000V, and base layer structure is exposed to CdCl
2Be heated to 650 ℃ in the mist of steam and dry air, and be incubated 10 minutes, then cool to room temperature.The characteristic that CdTe is not affected by the nitrogen doping substantially because ZnTe more easily forms the doping of high concentration p-type forms the heavy p-type ZnTe:N nanometer dipole particle that nitrogen adulterates in CdTe photovoltaic medium.
Then with CdCl
2Nanometer dipole particle solar battery thin film base layer structure after heat treatment sent into the vacuum chamber of this sputtering equipment, puts into 99.99% High Purity Gold in evaporator crucible; Vacuumize and reach lower than 4 * 10
-4Pa; Open heating power supply to the evaporator crucible power supply until gold dissolves; Open baffle plate to glass substrate hydatogenesis gold, thickness is 600nm, prepares the second conductive electrode layer, completes the battery preparation.
High-purity ZnO:Al target of 99.999% is installed on the target position of magnetron sputtering apparatus; Then the glass substrate of cleaning is sent into the vacuum chamber of thermal evaporation apparatus, and be heated to 200 ℃; Vacuum chamber is evacuated to lower than 4 * 10
-4Pa; Be filled with argon gas in vacuum chamber to 2Pa; Open the radio frequency sputtering power supply, regulate this output power of power supply to 2.5W/cm
2, the distance between target and glass substrate is 10cm; The thick ZnO:Al transparent conductive film (TCO) of sputtering sedimentation 1.0 μ m, i.e. the first transparency conductive electrode layer under these process conditions.
After the ratio of 1: 20 is mixed in mass ratio with CdS and CdTe, at 1000N/cm
2Pressure under be pressed into the hybrid target material, the target that this composite material is made is installed on the target position of magnetron sputtering apparatus; Then the TCO Conducting Glass is sent into the vacuum chamber of this sputtering equipment, and be heated to 250 ℃; Vacuum chamber is evacuated to lower than 4 * 10
-4Pa; Be filled with argon gas in vacuum chamber to 2Pa; Open the radio frequency sputtering power supply, regulate this output power of power supply to 2.5W/cm
2, the distance between target and glass substrate is 10cm; The thick CdSTe alloy firm of sputtering sedimentation 5 μ m under these process conditions is made nanometer dipole particle solar battery thin film base layer structure 150.
Nanometer dipole particle solar battery thin film base layer structure 150 is placed in CdCl
2Dry air in be heated to 650 ℃, and be incubated 5 minutes, then cool to room temperature.
Then with CdCl
2Nanometer dipole particle solar battery thin film base layer structure after heat treatment sent into the vacuum chamber of this sputtering equipment, puts into 99.99% High Purity Gold in evaporator crucible; Vacuumize and reach lower than 4 * 10
-4Pa; Open heating power supply to the evaporator crucible power supply until gold dissolves; Open baffle plate to glass substrate hydatogenesis gold, thickness is 600nm, prepares the second conductive electrode layer, completes the battery preparation.
Embodiment 4
The glass substrate of cleaning is sent into the vacuum chamber of thermal evaporation apparatus, put into 99.99% High Purity Gold in evaporator crucible; Vacuumize and reach lower than 4 * 10
-4Pa; Open heating power supply to the evaporator crucible power supply until gold dissolves; Open baffle plate to glass substrate hydatogenesis gold, thickness is 600nm.Complete the preparation of the second conductive electrode layer.
After the ratio of 1: 20 is mixed in mass ratio with CdS and CdTe, at 1000N/cm
2Pressure under be pressed into the hybrid target material, the target that this composite material is made is installed on the target position of magnetron sputtering apparatus; The glass substrate that then will deposit gold thin film is sent into the vacuum chamber of this sputtering equipment, and is heated to 250 ℃; Vacuum chamber is evacuated to lower than 4 * 10
-4Pa; Be filled with argon gas in vacuum chamber to 2Pa; Open the radio frequency sputtering power supply, regulate this output power of power supply to 2.5W/cm
2, the distance between target and glass substrate is 10cm; The thick CdSTe alloy firm of sputtering sedimentation 2.0 μ m under these process conditions is made nanometer dipole particle solar battery thin film base layer structure.
The second conductive electrode layer of the nanometer dipole particle solar battery thin film base layer structure that will be made of substrate, the second conductive electrode layer and photovoltaic effect layer-gold thin film adds the direct voltage of 10V, and base layer structure is placed in CdCl
2Dry air in be heated to 550 ℃, and be incubated 90 minutes, then cool to room temperature.
Complete CdCl
2After heat treatment, preparation the first transparency conductive electrode layer on solar cell is completed the battery preparation.High-purity ZnO:Al target of 99.999% is installed on the target position of magnetron sputtering apparatus; Then with CdCl
2Nanometer dipole particle solar battery thin film base layer structure after heat treatment sent into the vacuum chamber of this sputtering equipment, and is heated to 200 ℃; Vacuum chamber is evacuated to lower than 4 * 10
-4Pa; Be filled with argon gas in vacuum chamber to 2Pa; Open the radio frequency sputtering power supply, regulate this output power of power supply to 2.5W/cm
2, the distance between target and glass substrate is 10cm; The thick ZnO:Al transparent conductive film of sputtering sedimentation 1.0 μ m, make nanometer dipole particle solar cell under these process conditions.
High-purity ZnO:Al target of 99.999% is installed on the target position of magnetron sputtering apparatus; Then send into the vacuum chamber of this sputtering equipment at the bottom of the stainless steel lining with cleaning, and be heated to 400 ℃; Vacuum chamber is evacuated to lower than 4 * 10
-4Pa; Be filled with argon gas in vacuum chamber to 2Pa; Open the radio frequency sputtering power supply, regulate this output power of power supply to 2.5W/cm
2, the distance between at the bottom of target and stainless steel lining is 10cm; The thick ZnO:Al transparent conductive film (TCO) of sputtering sedimentation 1.0 μ m, i.e. the first transparency conductive electrode layer under these process conditions.
After the ratio of 1: 20 is mixed in mass ratio with CdS and CdTe, at 1000N/cm
2Pressure under be pressed into the hybrid target material, the target that this composite material is made is installed on the target position of magnetron sputtering apparatus; Then send into the vacuum chamber of this sputtering equipment at the bottom of having deposited the stainless steel lining of ZnO:Al, and be heated to 300 ℃; Vacuum chamber is evacuated to lower than 4 * 10
-4Pa; Be filled with argon gas in vacuum chamber to 2Pa; Open the radio frequency sputtering power supply, regulate this output power of power supply to 2.5W/cm
2, the distance between at the bottom of target and stainless steel lining is 10cm; The thick CdSTe alloy firm of sputtering sedimentation 20 μ m under these process conditions is made nanometer dipole particle solar battery thin film base layer structure.
Nanometer dipole particle solar battery thin film base layer structure is placed in CdCl
2Dry air in be heated to 650 ℃, and be incubated 5 minutes, then cool to room temperature.
Then with CdCl
2Nanometer dipole particle solar battery thin film base layer structure after heat treatment sent into the vacuum chamber of the sputtering equipment that installs high-purity ZnO:Al target of 99.999%, and is heated to 400 ℃; Vacuum chamber is evacuated to lower than 4 * 10
-4Pa; Be filled with argon gas in vacuum chamber to 2Pa; Open the radio frequency sputtering power supply, regulate this output power of power supply to 2.5W/cm
2, the distance between at the bottom of target and stainless steel lining is 10cm; The thick ZnO:Al transparent conductive film of sputtering sedimentation 1.0 μ m, make nanometer dipole particle solar cell on opaque substrate under these process conditions.
At first prepare nanometer dipole particle solar battery thin film base layer structure 150.After the ratio of 1: 2.5 is mixed in mass ratio with CdS and CdTe, at 6000N/cm
2Pressure under be pressed into the hybrid target material, the target that this composite material is made is installed on the sputter target position of magnetron sputtering apparatus; The glass substrate (TCO glass) that then will be coated with the first transparency conductive electrode layer is sent into the vacuum chamber of this sputtering equipment, and is heated to 250 ℃; Vacuum chamber is evacuated to lower than 4 * 10
-4Pa; Be filled with argon gas in vacuum chamber to 2Pa; Open the radio frequency sputtering power supply, regulate its power output to 2.5W/cm
2, the distance between target and glass substrate is 10cm; The thick CdSTe alloy firm of sputtering sedimentation 20 μ m under these process conditions is made nanometer dipole particle solar battery thin film base layer structure 150.
Fig. 5 D has provided through applying the CdCl of polarization field
2Electric dipole after processing is arranged in the same way.Wherein the electric dipole arrangement can be also rightabout.As shown in Fig. 5 D, nanometer dipole particle solar battery thin film base layer structure 150 can be at electric field-enhanced CdCl
2Form the higher nanometer dipole particle solar cell 150 of polarizability in Technology for Heating Processing 170 ".Electric field-enhanced CdCl
2Treatment process 170 is similar to CdCl
2Treatment process 160, but carrying out CdCl
2Apply polarized electric field when processing on the first transparency conductive electrode layer 114, intensity is 3000V.Polarized electric field is applied on the first transparency conductive electrode layer 114, forms more consistent arrangement in the same way thereby drive CdS electric dipole 200 in photovoltaic medium 122.Complete CdCl
2After heat treatment (as 160 or 170), preparation the second conductive electrode layer on solar cell is completed the battery preparation.
Figure 6 shows that the performance of the nanometer dipole particle solar cell of embodiment 1 preparation, compared plane p-n junction battery (conventional batteries) 135 and the quantum efficiency of described nanometer dipole particle solar cell (mixed film) 136 and the relation of wavelength in Fig. 6.Spectral band is 430～850nm.Fig. 6 has provided glass substrate and tco layer to the impact of solar cell integrated efficient, and they can absorb the light (glass absorption portion 133, TCO absorption portion 134) that a part enters their inside, has therefore reduced battery efficiency.Yet the nano particle solar cell is compared the planar junction battery table high energy part (being the shortwave strong point, about 430～550nm wave band) 137 of incident light and has been revealed very strong improvement.Plane p-n junction battery is that absorption due to CdS N-shaped layer causes in the loss 138 of this wave band.Therefore can convert more light to electricity, this improve final body present in the output of battery.
Fig. 7 A has provided the measurement data of the solar cell of several groups of the present invention's preparations to 9B, with explanation CdCl
2Treatment process reaches the impact of plane solar energy battery (Fig. 7 B, 8B and the 9B) performance that does not contain the nanometer dipole, CdCl on nanometer dipole particle solar cell
2Treatment process on the impact of nanometer dipole particle solar cell properties as shown in Fig. 7 A, 8A and 9A, CdCl
2Treatment process on the impact of the plane solar energy battery performance that do not contain the nanometer dipole as shown in Fig. 7 B, 8B and 9B.As shown in Figure 7, the mean value of solar battery efficiency is through CdCl
2All promote to some extent after processing.Also find out from figure, at every turn through CdCl
2After processing, nanometer dipole particle solar cell is compared and is not contained nanometer dipole planar junction battery and all shown narrower with more consistent efficiency distribution, two kinds of samples have shown the efficient (6% and 3.3%) that almost differs one times, and the yields of nanometer dipole particle solar cell reaches 100%.Therefore, nano particle solar cell large-scale production preferably.
Fig. 8 A and 8B have provided CdCl
2The impact of processing time on battery open circuit voltage (Voc).Obviously find out from figure, the open circuit voltage of the nano particle solar cell shown in Fig. 8 A is high more a lot of than the open circuit voltage of the planar junction solar cell shown in Fig. 8 B.And two kinds of batteries are at given CdCl
2Under processing time, shown the short circuit current that approaches.
Figure 10 has compared the relation between the square value of the projectile energy of planar junction and nano particle solar cell and absorption coefficient and projectile energy product, has comprised CdCl
2Situation before and after processing.Absorption coefficient determines the injection degree of depth of light in solar cell of specific wavelength.Therefore, high absorption coefficient illustrative material can absorb more luminous energy.To direct band gap material (as CdTe, CdS), when the long-pending quadratic sum incident energy the relationship between quantities of pressing absorption coefficient and projectile energy was mapped, curve can provide linear segment.The intercept of linear segment on energy axes is the band gap of this material.Band gap has characterized the required minimum photon energy that produces the free electron generating, therefore means the absorption threshold value.What low band gaps material or structure were compared high band gap can utilize the wider spectrum of scope.
Figure 10 has provided the nano solar battery at CdCl
2Absorbance curves 250 before processing.Curve 250 does not provide the clear and definite range of linearity and does not provide very strong ABSORPTION EDGE.Therefore, absorbing threshold value is gradual change, and this has limited the ability of battery absorption incident power generation free electron.Curve group 260 has shown CdCl
2Processing is key to the nano particle solar cell.Sharp-pointed ABSORPTION EDGE is exactly evidence, illustrates that band gap is approximately 1.486eV.By comparing, the curve group 270 that does not contain the planar junction battery of nanometer dipole has provided the similar range of linearity and clear and definite ABSORPTION EDGE has been arranged, but band gap is higher, is approximately 1.50eV.
Figure 11 has described the current-voltage performance test curve that uses CdS nanometer dipole particle battery that the inventive method prepares, and as an instantiation, its preparation method as mentioned above.Although there is no the p-n junction structure in battery, the I-V characteristic of diode is obvious.In this explanation battery, the granuloplastic polarized electric field of electric dipole has played the one-way conduction effect same with the p-n junction electric field.The concrete test performance of this battery is:
Test condition is:
Spectrum AM1.5G
Light intensity 100mW/cm
2
25 ℃ of battery temperatures.
Use the piezoelectric forces microscope to characterize the sample of solar cell of the present invention, its method is: install conducting probe in the piezoelectric forces microscope, and control system is adjusted to measurement pattern; The sample of solar cell of the present invention is put under the microscopical conducting probe of piezoelectric forces, and probe is added the alternation oscillating voltage, then record surperficial each coordinate position probe of battery sample with length travel and the teeter information of oscillating voltage; When collecting each coordinate position probe of described battery sample surface with the length travel of oscillating voltage and teeter information, the probe that uses lock-in amplifier (Lock-in Amplifier) to process to obtain from the microscopical light sensor of piezoelectric forces is with length travel and the teeter signal of oscillating voltage, therefrom filter out the signal with oscillating voltage source same frequency, remove noise.Solar cell surface of the present invention is scanned, and draw out the length travel of battery thin film surface each point or teeter signal with the distribution map of corresponding probe coordinate; The local deformation of nanometer dipole particle and the phase difference between oscillating voltage can provide the local polarisation directional information of electric dipole particle, and the corresponding probe coordinate of phase difference is drawn out the vectorial piezoelectric effect distribution map of film.
Figure 12 A, Figure 12 B describes is longitudinal piezoelectric effect (Vertical PFM) by piezoelectric forces microscope (Piezoresponse Force Microscopy), be Figure 12 A, and piezo-electric traverse effect (Lateral PFM), be Figure 12 B, scanning obtains size, the distributed intelligence of nanometer dipole particle.Same equipment can also obtain the information of the local polarisation direction distribution of electric dipole by vectorial piezoelectric effect (Vector PFM) scanning.Its principle is, 300 pairs of film surfaces of conducting probe by the piezoelectric forces microscopic system under contact mode apply an oscillating voltage 320, can produce the deformation concussion of same frequency due to the piezoelectric property of nanometer dipole particle 120 under the impact of this local biases, not have the photovoltaic dielectric material 122 of piezoelectric property can not change.Therefore solar cell surface of the present invention is scanned, the position that coordinates the AFM scan-probe, and draw out the length travel of battery thin film surface each point or teeter signal with the distribution map of corresponding probe coordinate, can distinguish nanometer dipole particle and photovoltaic dielectric material, and obtain the information such as distribution, size, shape, electric dipole moment of nanometer dipole particle.Draw the distribution map of the local deformation probe coordinate corresponding with phase difference between oscillating voltage, i.e. vectorial piezoelectric effect distribution map can provide the information of the electric dipole moment direction of electric dipole particle.
Nanometer dipole particle can cause the longitudinal oscillation of probe when flexible, produces longitudinal piezoelectric effect figure, i.e. Figure 12 A; Can cause the probe teeter during tangential deformation, and produce piezo-electric traverse effect figure, be i.e. Figure 12 B.Oscillation Amplitude is directly proportional to polar intensity.The length travel of probe and teeter can by the PFM system four mutually light sensor 310 amplify and obtain, and record the formation scintigram.And the polarised direction of nanometer dipole particle and applying bias field direction be when inconsistent, and the phase place of deformation has and relatively lags behind, so this phase difference can provide the information of electric dipole polarised direction, is called vectorial piezoelectric effect figure.Therefore, this method can also provide the polarised direction of each nanometer dipole particle, is macroscopical output characteristic (as open circuit voltage) of setting up this battery and the distribution of its microstructure and electric dipole, the quantitative relationship between polarised direction.
Claims (7)
1. a nanometer dipole solar cell, comprise substrate layer (112), the first transparency conductive electrode layer (114), photovoltaic effect layer (116) and the second conductive electrode layer (118); The position relationship of described each layer with sunlight enter arranged sequentially, be followed successively by the first transparency conductive electrode layer (114), photovoltaic effect layer (116), the second conductive electrode layer (118), it is characterized in that described photovoltaic effect layer (116) is made of jointly the material with photovoltaic effect and the nanometer dipole particle that is embedded in the photovoltaic effect material, described nanometer dipole particle has polarization or piezoelectric properties; When substrate layer (112) was made for transparent material, substrate layer (112) was positioned at the first transparency conductive electrode layer (114) before; When being made of opaque material, substrate layer (112) is positioned at the second conductive electrode layer (118) afterwards when substrate layer (112).
2. nanometer dipole solar cell as claimed in claim 1, it is characterized in that, in described photovoltaic effect layer (116), described nanometer dipole particle is a kind of in p-type or N-shaped semi-conducting material, and the photovoltaic dielectric material is the another kind in p-type or N-shaped material; In photovoltaic effect layer (116), each nanometer dipole particle produces an electric dipole.
3. nanometer dipole solar cell as described in claim 0 or 0, it is characterized in that and at least part of in the same way arrangement polarized at described nanometer dipole particle, nanometer dipole particle polarised direction is important on the direction perpendicular to transparency conductive electrode layer or conductive electrode layer.
4. nanometer dipole solar cell as claimed in claim 1 or 2, is characterized in that at described nanometer dipole particle by CdS or CdS
xTe
(1-x)Alloy consists of, x=0～1; Described photovoltaic dielectric material is made of CdTe.
5. prepare the preparation method of the described nanometer dipole of claim 0 solar cell, it is characterized in that described method comprises following steps:
A) cleaning is coated with the glass substrate of described the first transparency conductive electrode layer or described the second conductive electrode layer, then the mixed film of sputtering sedimentation CdTe and CdS on described glass substrate, described film thickness scope is 0.2-20 μ m, the target that uses as CdS and CdTe in mass ratio 1: 30-1: compacting after 2.5 scopes are mixed;
The glass substrate that b) will deposit CdTe and CdS mixed film is placed in CdCl
2With in the mixed-gas atmosphere of air heat treatment 5-120 minute, heating-up temperature was 350～650 ℃;
C) at CdCl
2Film surface after heat treatment re-uses sputtering method described the first transparency conductive electrode layer of deposition or described the second conductive electrode layer, forms described solar cell.
6. preparation method as claimed in claim 5, it is characterized in that when implementing described step 0 and step 0, apply polarized electric field on described the first transparency conductive electrode layer or described the second conductive electrode layer, voltage is 10～3000V, and the CdTe and the CdS mixed film that deposit are placed among electric field.
7. the method for the macro property of a quantization signifying nano particle solar cell claimed in claim 1 and its microstructure and polarization characteristic Relations Among, it is characterized in that, described method is by longitudinal piezoelectric effect and the piezo-electric traverse effect of the described solar cell of scanning survey, evidence and the distributed intelligence that the nanometer dipole exists sought in scanning, the information that the local polarisation direction that obtains electric dipole by vectorial piezoelectric effect scanning simultaneously distributes, step is as follows:
A) the microscopical probe of piezoelectric forces is replaced by conducting probe and adjusts to the contact measurement pattern, and conducting probe is applied the alternation oscillating voltage, to described solar cell sample surface scan, and record the probe of each coordinate position with length travel and the teeter information of oscillating voltage;
B) the solar cell sample surface information that a) obtains according to step, draw out the length travel of described solar battery thin film surface each point or teeter signal with the distribution map of corresponding probe coordinate, distinguish nanometer dipole particle and photovoltaic dielectric material, and obtain the information such as the size of distribution, size, shape, electric dipole moment of nanometer dipole particle and polarizability;
C) according to step b) obtain the local deformation of nanometer dipole and the phase difference between oscillating voltage, the electric dipole moment polarised direction information of electric dipole particle is provided, and corresponding probe coordinate is drawn out the vectorial piezoelectric effect distribution map of described solar battery thin film;
D) size, polarizability and the direction of the electric dipole moment of the nanometer dipole particle of measurement solar cell of the present invention.
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