CN101326676A - Photoelectric conversion element and solar cell using same - Google Patents

Photoelectric conversion element and solar cell using same Download PDF

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CN101326676A
CN101326676A CN 200680046410 CN200680046410A CN101326676A CN 101326676 A CN101326676 A CN 101326676A CN 200680046410 CN200680046410 CN 200680046410 CN 200680046410 A CN200680046410 A CN 200680046410A CN 101326676 A CN101326676 A CN 101326676A
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semiconductor layer
porous semiconductor
mist degree
layer
light
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CN100588028C (en
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千叶恭男
韩礼元
小出直城
城户政美
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Sharp Corp
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Abstract

A photoelectric conversion element having improved photoelectric conversion efficiency is provided. Furthermore, a solar cell employing such photoelectric conversion element is also provided. The photoelectric conversion element is composed of a photoelectric conversion layer (31) composed of a porous semiconductor layer (11) adsorbing dye, a carrier transporting layer (4) and a pair of electrodes (3, 7). The total haze ratio of the porous semiconductor layer (11) of the photoelectric conversion layer (31) in a near infrared region is 60% or more but not more than 95%. Especially when the porous semiconductor layer (11) is composed of a plurality of layers, the haze ratio of the porous semiconductor layer in the near infrared region furthest from a light incoming side is preferably 60% or more but not more than 95%.

Description

Photo-electric conversion element and use the solar cell of this photo-electric conversion element
Technical field
The present invention relates to photo-electric conversion element and use the solar cell of this photo-electric conversion element.
Background technology
Solar cell utilizes sunlight to replace fossil fuel as the energy, has carried out many relative researchs.At present, the main flow of practicability solar cell is monocrystalline, polycrystalline or amorphous (amorphous) silicon, and the energy cost height in its material cost and the manufacturing process has hindered popularizing of solar cell to a great extent.
On the other hand, as novel solar battery, Te Kaiping 1-220380 communique (patent documentation 1), international disclosing in the WO94/05025 communique (patent documentation 2) etc. as the photo-electric conversion element of the photic electron transfer that utilizes metal complex, disclose dye-sensitized solar cell.
This type of dye-sensitized solar cell is made up of following part: the photoelectric conversion layer, carrier transport layer and the pair of electrodes that are made of the porous semiconductor layer that has adsorbed dyestuff.In porous semiconductor layer,, two pyridine ruthenium complex have been adsorbed as the sensitizing dye that has absorption spectrum in the visible region.
In this type of battery, if the photoelectric conversion layer that is made of porous semiconductor layer and dyestuff with rayed, then the electronics in the dyestuff is excited, and this electronics moves to antipole by external circuit.Moving to the electronics of antipole, is that photoelectric conversion layer is returned in the transportation of the ion in the electrolyte by carrier transport layer.Such process is gone round and begun again, the output electric energy.Yet, to compare with silicon solar cell, the present situation of dye-sensitized solar cell still rests on the low photoelectric conversion efficiency stage.
Wherein, open the spy that to disclose following in the 2000-106222 communique (patent documentation 3) be the technology of target to improve photoelectric conversion efficiency: in porous semiconductor layer, mix and use the different particle of particle size distribution.
In addition, the spy opens flat 10-255863 communique (patent documentation 4) to disclose following is the technology of target to improve photoelectric conversion efficiency: stacked 2 layers of titanium oxide.
In addition, the spy opens 2002-222968 communique (patent documentation 5) to disclose following is the technology of target to improve photoelectric conversion efficiency: the stacked porous semiconductor layer that is made of the different particle of particle diameter.
In addition, the spy opens 2003-217689 communique (patent documentation 6) to disclose following is the technology of target to improve photoelectric conversion efficiency: the mist degree that is controlled at visible region.
Patent documentation 1: the spy opens flat 1-220380 communique
Patent documentation 2: the international WO94/05025 communique that discloses
Patent documentation 3: the spy opens the 2000-106222 communique
Patent documentation 4: the spy opens flat 10-255863 communique
Patent documentation 5: the spy opens the 2002-222968 communique
Patent documentation 6: the spy opens the 2003-217689 communique
Summary of the invention
Invent problem to be solved
Yet, in the method for above-mentioned patent documentation 3～6, have following problems.Usually, if the oxide semiconductor particle is heated, then this particle can raise with temperature and grow, and understands between the also known particle further combined with, and gigantism.That is, even form porous semiconductor layer with the particle of having controlled particle diameter, particle also can gigantism in heating process, so the particle size distribution of its porous semiconductor layer and the optical characteristics that accompanies with it have uncertainty.
Owing to above reason, even as above-mentioned patent documentation 3, only the titanium oxide particle diameter in the porous semiconductor layer material solution (or suspension) is adopted methods such as SEM, X-ray diffraction to measure and stipulate, semi-conductive particle size distribution behind the formation porous semiconductor layer is also different because of the formation condition of this porous semiconductor layer, therefore may not obtain high-photoelectric transformation efficiency.
In addition, also be to use the material solution (or suspension) of only having stipulated the titanium oxide particle diameter to form light reflective particle layer in patent documentation 4 equally, the particle size distribution in the light reflective particle layer of formation is uncertain, and light reflectivity has uncertainty.Therefore, may not obtain high-photoelectric transformation efficiency.
And, also have following description in the patent documentation 4: " (titanium oxide in the suspension) particle diameter being controlled at the scope of about 200～500nm, ", and this particle diameter ", being 1.3 * π/K " with respect to the wave number K of light so that light scattering reaches maximum.By above 2 as can be known: so-called " light " that is used to improve photoelectric conversion efficiency in patent documentation 4, its wave-length coverage comprises visible region and a part of ultraviolet light of about 310～770nm.
In addition, in above-mentioned patent documentation 5, for improving photoelectric conversion efficiency, stipulated the particle diameter of the semiconductor particle in the material solution (or suspension) of porous semiconductor layer, and the scattering of having stipulated the porous semiconductor layer in the visible region in view of the above, but as above-mentioned, optical property (herein being scattering) is different because of the formation condition of porous semiconductor layer, and photoelectric conversion efficiency also changes because of manufacturing conditions.
Above-mentioned patent documentation 6 has been introduced the notion of the mist degree of visible region aspect porous semiconductor layer.This has improved the quantum yield of visible region, and it is effectively as the method that improves exchange efficiency, but can't obtain higher conversion efficiency.
The method of dealing with problems
The present inventor has carried out the improvement of porous semiconductor layer character for realizing the efficiency light electric transition element, in this process, we notice the optical property of porous semiconductor layer in the near infrared region, find: by stipulating the mist degree of this semiconductor in the near infrared region, can obtain to have the photo-electric conversion element of good electricity conversion, thereby finish the present invention.That is, the invention provides:
1. photo-electric conversion element, it comprises photoelectric conversion layer, carrier transport layer and the pair of electrodes of being made by the porous semiconductor layer that has adsorbed dyestuff, wherein, the mist degree of the described porous semiconductor layer of described photoelectric conversion layer in the near infrared region is 60%～95%;
2. above-mentioned 1 photo-electric conversion element, wherein, described porous semiconductor layer is by constituting at the different a plurality of layers of near infrared region mist degree;
3. above-mentioned 2 photo-electric conversion element, wherein, the porous semiconductor layer that the mist degree that described porous semiconductor layer is included in the near infrared region increases successively from the light incident side of light;
4. above-mentioned 3 photo-electric conversion element wherein, in the described porous semiconductor layers that are made of described a plurality of layer, is 60%～95% apart from the mist degree of light incident side described porous semiconductor layer farthest in the near infrared region of light;
5. above-mentioned 4 photo-electric conversion element, wherein, described porous semiconductor layer is 3 layers, and, porous semiconductor layer the mist degree near infrared region nearest apart from the light incident side of light is more than 1% and less than 11%, is 60%～95% apart from the mist degree of light incident side porous semiconductor layer farthest in the near infrared region of light;
6. above-mentioned 4 photo-electric conversion element, wherein, described porous semiconductor layer is 4 layers, and, porous semiconductor layer the mist degree near infrared region nearest apart from the light incident side of light is more than 1% and less than 11%, is 60%～95% apart from the mist degree of light incident side porous semiconductor layer farthest in the near infrared region of light;
7. above-mentioned 1～6 each photo-electric conversion element, wherein, it is the oxide semiconductor of principal component that described porous semiconductor layer comprises with the titanium oxide;
8. above-mentioned 1～7 each photo-electric conversion element, wherein, described mist degree is the value of measuring in the random wave strong point of 780nm～900nm;
9. solar cell, it has used 1～8 each a photo-electric conversion element.
The invention effect
According to the present invention, in the photo-electric conversion element that constitutes in the photoelectric conversion layer that constitutes by the porous semiconductor layer that has adsorbed dyestuff, carrier transport layer and pair of electrodes, making the mist degree of porous semiconductor layer integral body in the near infrared region is 60%～95%, can improve the photoelectric conversion efficiency of photo-electric conversion element.When porous semiconductor layer is sandwich construction, be 60%～95% particularly, can improve the photoelectric conversion efficiency of photo-electric conversion element by making apart from the mist degree of light incident side porous semiconductor layer farthest in the near infrared region of light.
Description of drawings
Fig. 1 is a sectional view, has shown the structure of the photo-electric conversion element of making among preferred photo-electric conversion element of the present invention and the embodiment.
Fig. 2 is a sectional view, has shown that photoelectric conversion layer is the structure of 3 layers photo-electric conversion element.
Fig. 3 is a sectional view, has shown that photoelectric conversion layer is the structure of 4 layers photo-electric conversion element.
Fig. 4 is a sectional view, has shown that photoelectric conversion layer is the structure of 5 layers photo-electric conversion element.
Fig. 5 is the pattern sectional view, and its making to the sample that is used for mist degree and measures is illustrated.
Fig. 6 is the pattern sectional view, and its making to the sample that is used for mist degree and measures is illustrated.
Fig. 7 is an ideograph, and it is illustrated the mensuration system that is used for mist degree mensuration.
Symbol description:
1 support; 2 conductive layers; 3,7 electrodes; 4 carrier transport layer; 5 base materials; 6 conductive layers; 11,11a, 11b, 11c, 11d, 11e porous semiconductor layer; 21 dividing plates; 22 encapsulants; 31 photoelectric conversion layers; 41,42 cross sections; 51 light sources; 52 wavelength selection systems; 53 specimen; 54 detectors; 55 reflecting plates; 56 slits; 61 light; 62 incident lights; The 63 parallel light that see through; 64 diffusions see through light; 65 all through light.
Embodiment
Below, describe with regard to suitable execution mode of the present invention.And following explanation only is exemplary, can implement in every way within the scope of the invention.
In conjunction with Fig. 1 embodiments of the present invention are described.Fig. 1 is a sectional view, has shown the structure of the photo-electric conversion element of making among preferred photo-electric conversion element of the present invention and the embodiment.That is, Fig. 1 shows dye-sensitized photoelectric conversion device.The structure of photo-electric conversion element shown in Figure 1 is as follows: form photoelectric conversion layer 31 on electrode 3, be filled with carrier transport layer 4 between electrode 3 and electrode 7, the structure of sealing by dividing plate 21 and sealing material 22 is adopted in the side; Wherein, described electrode 3 is made of conductive supporting member, and described photoelectric conversion layer 31 is made of the porous semiconductor layer that has adsorbed dyestuff, and described electrode 7 is made of electrode side support electrode 3.
Here, photoelectric conversion layer 31 is made of single or multiple lift porous semiconductor layer 11 and the dyestuff that is adsorbed in wherein.Among the present invention, " porous semiconductor layer " is meant the semiconductor layer that comprises many emptying apertures (being the space).
Below, each parts that uses in the photo-electric conversion element to Fig. 1 describe.
(conductive supporting member)
The conductive supporting member that forms electrode 3 among the present invention can followingly form: on the support of being made by transparent bases such as glass plate or plastic plates 1, tin indium oxide (ITO), tin oxide (SnO are set 2), zinc oxide transparency conducting layers such as (ZnO) is as conductive layer 2.
(mist degree)
The feature of porous semiconductor layer of the present invention is to have certain mist degree in the near infrared region.Thereby, at first mist degree is described.Usually, mist degree is meant: when having the light (for example standard sources D65, standard sources C) of spectrum when injecting specimen at visible region and/or near infrared region, the diffusion transmitance is divided by the value of total light penetration gained, and value that it is available 0～1 or 0～100% percentage are represented.
In invention, with conditional independences such as the number of plies of porous semiconductor layer 11, bed thickness, when the mist degree of measuring porous semiconductor layer 11 integral body (below be referred to as " total mist degree "), total light penetration and diffusion transmitance when measuring light from electrode 3 one side incidents that the incident light side promptly is made of the semiconductor support the photo-electric conversion element get final product.By device (for example, described device has and the close-connected integrating sphere of specimen, and the specimen opposition side at integrating sphere has ligh trap (magazine) or on-gauge plate simultaneously), can finish this mensuration simply with light source and actinometry unit.That is, be provided with under the state of on-gauge plate incident light light quantity T1 when measuring n.s and the total light light quantity T2 of seeing through when sample is arranged; Be provided with under the state of ligh trap, diffused light light quantity T3 that device sends when measuring n.s and the diffusion when sample is arranged see through light light quantity T4; Calculate total light penetration Tt=T2/T1, diffusion transmitance Td=[T4-T3 (T2/T1)]/T1, thus draw mist degree H=Td/Tt.
Usually, the lightsensitivity of dye-sensitized solar cell depends on the spectrum of dyestuff.For example, when using BlackDye (Solaronix company: ruthenium 620-1H3TBA, three (isothiocyanates)-rutheniums (II)-2,2 ': 6 ', 2 " pyridine-4-three, 4 '; 4 "-tricarboxylic acids three (4-butyl ammonium)) time, have the highest quantum yield near 600nm, in the wave-length coverage longer than 600nm, quantum yield increases with wavelength and reduces.Above-mentioned patent document 6 promptings: by improving the mist degree of visible region, can improve the quantum yield in the following wave-length coverage of 700nm, thereby improve the conversion efficiency of dye-sensitized solar cell.
But,, it is important further to improve the quantum yield of Long wavelength region in order to obtain higher conversion efficiency.
That is, in dye-sensitized solar cell, the photon in the long wavelength zone of a part of incident is not fully absorbed by photoelectric conversion layer 31 and sees through, and this is the low and low reason of dye-sensitized solar cell photoelectric conversion efficiency of near infrared region quantum yield.Discoveries such as the inventor: be closed at the transmitted light with this near infrared region on the problem of photoelectric conversion layer 31 inside, it is effective adopting the porous semiconductor layer 11 that has high mist degree in the near infrared region.
Among the present invention, " visible region " is defined as 380nm～780nm, and " near infrared region " is defined as 780nm～1200nm.In addition, the mist degree of the near infrared region of stipulating among the present invention is meant the mist degree in the random wave strong point of the near infrared region of above-mentioned definition.
Among the present invention, the porous semiconductor layer totally mist degree in the near infrared region is more than 60%.This mist degree is more than 60%, and then the effect at photoelectric conversion layer 31 inner sealing light is abundant, can obtain fully high photo-electric conversion element of photoelectric conversion rate.This mist degree is preferably more than 70%.On the other hand, porous semiconductor layer totally the mist degree in the near infrared region be below 95%.This mist degree then can fully guarantee the dyestuff adsorbance below 95%.In addition, in the near infrared region, especially preferably the overall mist degree of porous semiconductor layer at any wavelength of 780nm～900nm wave-length coverage is more than 60%, and is preferred more than 70%, and below 95%.
To the radiant intensity height of 900nm, therefore, controllable in the present invention porous semiconductor layer is preferably the haze value at any wavelength of 780nm～900nm wave-length coverage at the haze value of near infrared region to the sunlight spectrum of AM1.5 especially in the visible region.
Fig. 2 is a sectional view, has shown that photoelectric conversion layer is the structure of 3 layers photo-electric conversion element.Show below situation among Fig. 2:, adopt the photoelectric conversion layer 31 that constitutes by 3 layers of porous semiconductor layer 11a, 11b, 11c as the photoelectric conversion layer 31 that constitutes by porous semiconductor layer 11.In the present invention, can use the porous semiconductor layer 11 that constitutes by a layer with homogeneous mist degree, but the porous semiconductor layer 11 that is made of the different a plurality of layers of the such mist degree of as shown in Figure 2 porous semiconductor layer 11a, 11b, 11c is preferred, because its light sealing effect is good, photoelectric conversion rate is higher.
In addition, when for example such to porous semiconductor layer 11a, 11b, 11c, when the porous semiconductor layers 11 that are made of the different a plurality of layers of mist degree were set, following porous semiconductor layer 11 is preferred: the mist degree of near infrared region increased successively from light incident side.The reasons are as follows.
Usually, the porous semiconductor layer that mist degree is little, the dyestuff adsorbance is big but the light sealing effect is poor.On the other hand, the bulky grain that exists in the big porous semiconductor layer of mist degree, big emptying aperture are more, thereby the dyestuff adsorbance is little but the light sealing effect is good.Therefore, the porous semiconductor layer that mist degree is the little for example porous semiconductor layer 11a of Fig. 2 is arranged on light incident side like that, and the porous semiconductor layer that mist degree is big for example porous semiconductor layer 11c be arranged on position like that away from the illumination side, a large amount of dyestuffs that are adsorbed in the little mist degree layer at big mist degree layer generation scattering, the light of reflection are absorbed once more.Its result, the light sealing effect improves, and can obtain high optoelectronic conversion ratio.Therefore, in order further to improve the light sealing effect, particularly importantly improve apart from the mist degree of light incident side porous semiconductor layer (for example porous semiconductor layer 11c among Fig. 2) farthest.Be preferably more than 60% and below 95% apart from the mist degree of light incident side porous semiconductor layer farthest in the near infrared region.More preferably this mist degree is more than 70% and below 95%.
Among the present invention, when porous semiconductor layer 11 was made of a plurality of layers, the number of plies of this porous semiconductor layer 11 was preferably more than 2 layers, more preferably more than 3 layers, is preferably 3 layers and 4 layers especially.Certainly, can adopt the sandwich construction more than 5 layers further to improve photoelectric conversion efficiency.But the production cost of sandwich construction can increase, and should weigh the raising rate and the element production cost of photoelectric conversion efficiency, determines the suitable number of plies.Fig. 3 is a sectional view, has shown that photoelectric conversion layer is the structure of 4 layers photo-electric conversion element.Fig. 4 is a sectional view, has shown that photoelectric conversion layer is the structure of 5 layers photo-electric conversion element.Show below situation among Fig. 3:, adopt the photoelectric conversion layer 31 that constitutes by 4 layers of porous semiconductor layer 11a, 11b, 11c, 11d as the photoelectric conversion layer 31 that constitutes by porous semiconductor layer 11; And show below situation among Fig. 4: as the photoelectric conversion layer 31 that constitutes by porous semiconductor layer 11, adopt the photoelectric conversion layer 31 that constitutes by 5 layers of porous semiconductor layer 11a, 11b, 11c, 11d, 11e.
Among the present invention, especially preferably the porous semiconductor layer that is made of multilayer increases from the light entrance face side successively at the mist degree of near infrared region.For example, when the number of plies of porous semiconductor layer 11 is 3 layers or 4 layers, following situation is preferred: the mist degree of near infrared region, in near the porous semiconductor layer of light incident side is more than 1% and less than 11%, the nearest porous semiconductor layer of distance light incident side and apart from light incident side farthest the mist degree in the intermediate layer between the porous semiconductor layer increase successively with the distance of distance light incident side, apart from light incident side farthest the mist degree of porous semiconductor layer be more than 60% and below 95%.More particularly, when for example the number of plies of porous semiconductor layer 11 is 3 layers, following situation is preferred: from the nearest layer of distance light incident side, the mist degree of near infrared region is followed successively by: ground floor is more than 1% and less than 11%, the second layer is more than 2% and less than 70%, the 3rd layer more than 3% and below 95%, and the overall mist degree of porous semiconductor layer 11 is more than 60% and below 95%.In addition, mist degree is more than 1% and less than 11% at ground floor preferably, is more than 11% and less than 70% at the second layer, is more than 70% and below 95% at the 3rd layer.
Below, introduce the evaluation method of the mist degree of porous semiconductor layer 11 of the present invention.The mist degree of porous semiconductor layer can adopt following method to measure: make the method for light from the direction incident vertical with this porous semiconductor layer 11, or make the method for light from horizontal direction incident.
When porous semiconductor layer 11 is made of a plurality of layer, can at first make light from the direction incident vertical with a plurality of layers porous semiconductor layer 11, measure total mist degree, successively subdue the mist degree of measuring each layer then.For example, the porous semiconductor layer 11 that can increase successively from the light incident side mist degree with reference to conduct is 3 layers a situation as shown in Figure 2.
At first, measure porous semiconductor layer 11a, this total mist degree of 3 layers of 11b, 11c.Then, the porous semiconductor layer 11c that cancellation is the 3rd layer, only on the electrode 3 that constitutes by conductive supporting member, keep the 1st layer (being porous semiconductor layer 11a) and the 2nd layer (porous semiconductor layer 11b), can measure total mist degree like this by 2 layers of porous semiconductor layer that constitutes.At this moment, porous semiconductor layer 11a, 11b, this total mist degree of 3 layers of 11c can be considered as the mist degree of the 3rd layer porous semiconductor layer 11c.Further, the porous semiconductor layer 11b that cancellation is the 2nd layer only keeps the 1st layer (being porous semiconductor layer 11a) on conductive supporting member, can measure its mist degree like this.At this moment, this total mist degree of 2 layers of porous semiconductor layer 11a, 11b can be considered as the mist degree of the 2nd layer porous semiconductor layer 11b.Method as the cancellation porous semiconductor layer does not have particular restriction, can adopt the whole bag of tricks, for example uses with sand paper, wet-strong paper, water file, cloth and files the file tool as representative, perhaps can use grinder, various grinding machines etc.At this moment, preferably use SEM or light microscope etc. to confirm the bed thickness of each layer in advance.
Below, the method that makes light measure mist degree from the direction incident vertical with porous semiconductor layer is carried out more specific description.
At the porous semiconductor layer 11 that is formed at the sandwich construction on the electrode 3 that constitutes by conductive supporting member
The vertical direction irradiates light of (considering 3 layers situation here) can be measured total mist degree like this.At this moment, preferably use SEM by the cross-section determination thickness in advance.
Then, can use the grinder cancellation apart from light incident side layer farthest, promptly be porous semiconductor layer 11c for 3-tier architecture shown in Figure 2., use SEM by cross-section determination thickness, can confirm to have formed porous semiconductor layer 11a, 11b thereafter.
The mist degree by porous semiconductor layer 11a, these 2 layers of porous semiconductor layers that constitutes of porous semiconductor layer 11b that remains can be measured by the vertical direction irradiates light at this porous semiconductor layer.Then, can use grinder cancellation porous semiconductor layer 11b., use SEM by cross-section determination thickness, can confirm to have formed porous semiconductor layer 11a thereafter.The mist degree of the porous semiconductor layer 11a that remains can be by measuring at the vertical direction irradiates light of this porous semiconductor layer 11a.
In addition, when porous semiconductor layer 11 is made of a plurality of layers, as the method that can estimate the mist degree of each layer more accurately, can followingly measure: for the porous semiconductor layer 11 that is formed at the sandwich construction on the electrode 3 that constitutes by conductive supporting member, from the direction vertical, promptly cut, carry out illumination from the horizontal direction of each layer along the bed thickness direction with its semiconductor surface.Section (the being cross-wise direction) thickness of this moment can carry out the thickness of each layer of affirmation for using SEM, light microscope etc. in advance.
Below, carry out the method that mist degree is measured in illumination at horizontal direction (promptly vertical direction) with the cross section from porous semiconductor layer, carry out specific description.
Use miniature cutter that porous semiconductor layer 11 is cut into suitable size on the vertical direction of semiconductor surface, as specimen; Described porous semiconductor layer 11 is made of a plurality of layer that is formed on the electrode 3, and described electrode 3 is made of conductive supporting member.At this moment, can dispose 2 samples that cut, feasible involutory as the porous semiconductor layer of tested object, use epoxy resin to fit, make 2 samples simultaneously.Then, can adopt the method for using disk grinder or chase grinder, perhaps adopt the method for using the laser scribing machine, carry out filming aptly.With the porous semiconductor layer 11 that cuts like this is sample, and each layer for it carries out illumination from the direction vertical with the cross section, can measure the mist degree of each layer.At this moment, the light that is used to measure mist degree can use optical collector etc. to shine each layer of porous semiconductor layer 11 respectively.
On the integrating sphere of combining closely with sample, width preferably is set and measures the identical or narrower slit of bed thickness of layer, the variable adjustable slit of slit width etc. perhaps is set than the bed thickness of this layer.And the light source as have luminescent spectrum in the near infrared region can list light sources such as xenon lamp, mercury xenon lamp, tungsten halogen lamp, or near ir laser etc.
Fig. 5, Fig. 6 are the pattern sectional view, and the making that is used for the sample that mist degree measures is illustrated.And, shown the situation when porous semiconductor layer is 3 layers among Fig. 6.Below, be that 3 layers situation is an example with porous semiconductor layer, measure the concrete grammar of mist degree and describe carry out illumination from the horizontal direction of porous semiconductor layer.
Use miniature cutter that porous semiconductor layer (, it constitutes by 3 layers) is cut along 2 cross sections (being cross section 41,42) with appropriate intervals shown in Figure 5 here, make sample shown in Figure 6; Described porous semiconductor layer 11 is made of a plurality of layer that is formed on the electrode 3, and described electrode 3 is made of conductive supporting member.With grinder this sample is carried out skiving, make that length is about 100 μ m between the cross section of this sample.And then, be about 10 μ m with grinder skiving to length between the cross section again, make specimen 53.
Fig. 7 is an ideograph, and it is illustrated the mensuration system that is used for mist degree mensuration.In order to measure the mist degree of each layer, can use mensuration system for example shown in Figure 7.As detector 54, can use the integrating sphere that has photomultiplier.As incident light, can use incident light 62, its be with the light 61 that 52 pairs of light sources 51 of wavelength selection system send carry out beam split and.Measure the wavelength that wavelength can be set to the near infrared region, be advisable with 800nm.
Can slit 56 be set before wavelength selection system 52, adjust suitable incident light.Light incident specimen 53 by slit 56.Reflecting plate 55 is set on integrating sphere, measures by the parallel light 63 that sees through and see through whole light 65 that see through that light 64 is formed, can calculate total light penetration like this with diffusion.In addition, take off reflecting plate 55, discharge the parallel light 63 that sees through, only measure diffusion and see through light 64, can calculate the diffusion transmitance like this.
Position between the layer to be measured of the opening of adjustment slit 56 and sample in cross section 41 can be measured total light penetration of porous semiconductor layer 11a, 11b, each layer of 11c respectively and spread transmitance.Measure by these, can obtain the mist degree of porous semiconductor layer 11a, 11b, each layer of 11c in the horizontal direction of each layer.In addition, when the vertical direction irradiation incident light time from the porous semiconductor layer 11 that is made of a plurality of layer, this mensuration system also can be used for the mensuration of mist degree.
The cross-wise direction thickness that is used for the sample that mist degree measures is being consistent being advisable of bed thickness (can with SEM etc. confirm in advance) of porous semiconductor layer with tested object.
On the other hand, when the bed thickness little (for example below the 5 μ m) of tested object, when sample is difficult to filming, can get the sample of suitable thickness (for example 10 μ m), the value that obtains is carried out bed thickness convert, being considered as tested object is the mist degree of porous semiconductor layer.One of bed thickness conversion method for example descends.
On the electrode of making by conductive supporting member 3, make porous semiconductor layer 11a, measure bed thickness and the total mist degree of this porous semiconductor layer 11a.Then, by identical manufacturing conditions (kind, coating condition, sintering condition that is suspension etc. is all identical), on porous semiconductor layer 11a, form porous semiconductor layer 11b, measure these 2 layers of porous semiconductor layer 11a and porous semiconductor layer 11b altogether bed thickness and total mist degree of 2 layers.Repeat the aforesaid operations of suitable number of times according to the number of plies of porous semiconductor layer 11, can obtain mist degree respectively corresponding to the different bed thickness of the porous semiconductor layer 11 under certain manufacturing conditions.Be made into chart, can derive the relational expression between bed thickness and the mist degree.By this relational expression, can carry out bed thickness convert (below, be called graphing method).
When being difficult to adopt said method to carry out number of plies conversion, promptly, because of being difficult to repeat the aforesaid operations of suitable number of times according to the number of plies of porous semiconductor layer 11, when mensuration can't be carried out thickness conversion corresponding to the mist degree of the different bed thickness of the porous semiconductor layer 11 under certain manufacturing conditions, can also adopt following method to carry out thickness conversion.For the porous semiconductor layers 11 that tested object promptly is made of a plurality of layer, make several (for example 2,3) samples, described sample has changed the length between the cross section of specimen 53.Length between this cross section can be estimated by the mode of using SEM etc. to carry out determining film thickness.By changing the length between the cross section, measure mist degree corresponding to each layer of the horizontal direction of length between different cross section.The mist degree of acquisition and the length between the cross section are made chart, can derive relational expression.Can carry out bed thickness by this relational expression converts.
In addition, measure mode as the mist degree among the present invention, can list following method: porous semiconductor layer 11 is in is formed on the electrode 3 that constitutes by conductive supporting member, and under this state, carry out method for measuring, porous semiconductor layer 11 is carried out method for measuring after the electrode 3 that is made of conductive supporting member is peeled off, on the electrode 3 that constitutes by conductive supporting member, form porous semiconductor layer 11 and seize porous semiconductor layer 11 on both sides by the arms by other support and carry out method for measuring.But, in view of the difficulty that peels porous semiconductor layer 11 from the electrode 3 that constitutes by conductive supporting member, and the influence of using other support to cause to mensuration, the state that porous semiconductor layer 11 is in be formed on the electrode 3 that is made of conductive supporting member is measured.
And, in order to measure the mist degree of porous semiconductor layer 11 exactly, preferably the dyestuff that is adsorbed in porous semiconductor layer 11 is carried out desorption after, measure again.The method of desorption dyestuff is for example: sample (promptly being formed at the photoelectric conversion layer 31 on the electrode 3 that is made of conductive supporting member) is immersed in the method in the aqueous solution of alkalescence, perhaps the above-mentioned aqueous solution is dropped in method on the above-mentioned sample etc.As alkaline aqueous solution, there is not particular restriction, preferred sodium hydrate aqueous solution, potassium hydroxide aqueous solution etc. are more preferably operated easier sodium hydrate aqueous solution.Concentration as alkaline aqueous solution is not particularly limited, as long as its pH greatly, is preferably pH10～14.
(porous semiconductor layer)
In the present invention, as obtaining the main method that has the porous semiconductor layer of certain mist degree in the near infrared region, for example can stipulate that its constituent material is the particle diameter of semiconductor particle (typically being metal oxide particle), dispersion condition when preparing the suspension that contains this semiconductor particle, the additive that adds in the coating condition of suspension, drying condition, sintering condition (being temperature and time) and the suspension, the kind (for example molecular weight) of tackifier, addition etc.
For example, by changing the temperature and time that hydro thermal method mesohigh still is handled, can control the particle diameter of semiconductor particle.In addition, can mix, and change mixing ratio, change average grain diameter by semiconductor particle with different-grain diameter.
In addition, dispersion condition when containing the suspension of this semiconductor particle as preparation, the time of application of the ball-milling method that adopts when for example preparing this suspension, coating succusion (ペ イ Application ト シ エ one カ one method), ultrasonic method etc., the diameter of perhaps dispersion usefulness pearl, material etc.
Coating condition as suspension, for example scrape the selection of the device of the skill in using a kitchen knife in cookery, spin-coating method, silk screen print method, such as the setting of screen thickness in the setting of rotary speed in the setting of scraping coating speed in the skill in using a kitchen knife in cookery, the spin-coating method, the silk screen print method, and the additive that comprises in the used suspension, solvent types and amount, this suspension properties is such as viscosity etc.
As the drying condition of suspension, can enumerate, for example baking temperature, drying time etc.As the sintering condition of suspension, can enumerate, for example the kind of the atmosphere gas when sintering temperature, sintering time, sintering, flow velocity etc.
At this, discoveries such as inventor: only stipulate in the above-mentioned condition such as the particle diameter of semiconductor particle in the suspension etc., can not determine the mist degree of the porous semiconductor layer made fully; And synthetically stipulate various conditions, can obtain to have the porous semiconductor layer 11 of certain haze value in the near infrared region.
And, as the material that constitutes porous semiconductor layer, can use in the known semiconductors such as titanium oxide, zinc oxide, tungsten oxide, barium titanate, strontium titanates, cadmium sulfate more than a kind or 2 kinds.This wherein, from the viewpoint of photoelectric conversion rate, stability, fail safe, preferred titanium oxide or zinc oxide are principal component.
As the method that on the electrode 3 that constitutes by conductive supporting member, forms porous semiconductor layer 11, can use various known methods.Concrete example as: coating contains the suspension of semiconductor particle, dry and sintering to form the method for porous semiconductor layer 11 on the electrode 3 that is made of conductive supporting member, on the electrode 3 that constitutes by conductive supporting member, wait the method that forms porous semiconductor layer 11, perhaps wait the method that forms porous semiconductor layer 11 etc. by PVD method, vapour deposition method, sputtering method or the sol-gel process of using raw material solid by CVD method or the mocvd method that uses needed raw material gas.And the bed thickness for these porous semiconductor layers 11 does not have particular restriction, but from viewpoints such as photopermeability, photoelectric conversion rates, is preferably about 0.5～50 μ m.
When forming the porous semiconductor layer 11 that constitutes by a plurality of layers, be that example describes for example with structure shown in Figure 2, then in said method, following method is preferred, because its cost is low: coating contains the suspension of semiconductor particle, dry and sintering to form the 1st layer is porous semiconductor layer 11a on the electrode 3 that is made of conductive supporting member, repeat coating, drying, the sintering step of suspension then, form the 2nd layer and later porous semiconductor layer 11b, porous semiconductor layer 11c successively.
As the manufacture method of semiconductor particle, for example firing method, sedimentation, hydro thermal method etc.This wherein, hydro thermal method is preferred, because this method can obtain the high-purity particle by using highly purified metal alkoxide raw material.
Can adopt ball-milling method, coating succusion, ultrasonic method etc. that above-mentioned semiconductor particle is dispersed in water or the organic solvent, come supending.
As the solvent that in above-mentioned suspension, uses, EGME classes such as glycol monoethyl ether (グ ラ イ system system) solvent, alcohols solvents such as ethanol, isopropyl alcohol, terpinol, mixed solvents such as iso-propanol/toluene, and water etc.In addition, preferably adopt method such as distillation that these solvents are carried out purifying before use.
As for improving the surfactant that stability of suspension adds, should use the organic class surfactant that decomposes in can the sintering process when forming porous semiconductor layer 11.At this moment, the preferred not surfactant of metal ion.As the not surfactant of metal ion, for example non-ionic surface active agent, fatty acid ammonium salt surfactant etc.As non-ionic surface active agent, ether type surfactant such as alkyl phenyl ether for example, ester type surfactants such as cithrol, nitrogenous type surfactant such as polyoxyethylene alkyl amine.In addition, for the viscosity of controlling suspension etc., can add polymer such as polyethylene glycol, polyvinyl alcohol, poly-ethyl cellulose.The molecular weight of these polymer, preferred 10000～300000.
Employing is scraped the suspension that the skill in using a kitchen knife in cookery, spin-coating method, silk screen print method etc. will make like this and is coated on the electrode 3 that is made of conductive supporting member, and dry, sintering form porous semiconductor layer 11.In addition, repeat to be coated with, the operation of dry, sintering, form the porous semiconductor layers 11 that constitute by a plurality of layers.
In the drying and sintering step of the suspension after coating, can adjust temperature, time, atmosphere gas etc. aptly according to the kind of the semiconductor particle in the suspension, conductive supporting member.For example, in air or in the non-active gas atmosphere, heating is 10 seconds～12 hours in 50～600 ℃ scope.Described drying and sintering can carry out more than 1 time or 2 times under a temperature, are perhaps carrying out more than 2 times under the different temperature.
(dyestuff)
Do not have particular restriction for the dyestuff that uses among the present invention, but it should be at least has absorption spectrum in the wavelength region may (being 200nm～10 μ m) of solar spectrum, and can discharge light activated electronics to porous semiconductor layer 11.
For example be fit to use N719 (suitable-two (isothiocyanates)-N, N '-two (2,2 '-two pyridines-4,4 '-dicarboxylic acids) ruthenium (II)), BlackDye (three (isothiocyanates)-rutheniums (II)-2,2 ': 6 ', 2 " pyridine-4,4-three; 4 "-tricarboxylic acids three (4-butyl ammonium)) ruthenium metalloid complex compound such as, azo dyes, quinones dyestuff, quinone imides dyestuff, quinacridine ketone dyestuff, side's acid (ス Network ア リ リ ウ system) class dyestuff, flower cyanine type dye, part flower cyanine type dye, triphenylmethane dye, xanthene class dyestuff, polyphiline class dyestuff ， perylene class dyestuff, phthalocyanines dye, the Coumarins dyestuff, organic dyestuff such as indigoid dyestuff.
In the present invention, there is not particular restriction for the method that makes dyestuff be adsorbed in porous semiconductor layer 11, can list some known methods, such as following method: above-mentioned dyestuff is dissolved in organic solvent prepares dye solution, the method of the porous semiconductor layer 11 in the gained dye solution on the dipping conductive supporting member, and the method for the gained dye solution being coated porous semiconductor layer 11 surfaces.And, before absorbing dye, can optionally carry out activation processing, for example heat treatment etc. to porous semiconductor layer 11 surfaces.
As the solvent of dissolving dye, as long as its energy dissolving dye has alcohols such as ethanol, ketones such as acetone particularly, ethers such as diethyl ether, oxolane, nitrogen-containing compound classes such as acetonitrile, chlorinated aliphatic hydrocarbons such as chloroform, aliphatic hydrocarbons such as hexane, aromatic hydrocarbon such as benzene, ester classes such as ethyl acetate, or the like.In addition, these solvents are preferably the solvent that adopts the known method purifying to cross, and can distill solvent before use and/or drying, with its purity of further raising.The concentration of dyestuff in the dye solution can suitably be adjusted according to used dyestuff, solvent species, dyestuff absorbing process etc., and for example 1 * 10 -5More than the mol, preferred 5 * 10 -5～1 * 10 -2Mol.
Porous semiconductor layer 11 impregnated in the adsorption method of dye solution, can be able to add dye solution in the suitable vessel of splendid attire porous semiconductor layer 11, then with the porous semiconductor layer mass-impregnation specified portions of impregnation porous semiconductor layer in this solution or only, and keep certain hour.The condition of this moment can be according to suitable adjustment such as used dyestuff, dissolving kind, solution concentrations.For example, the temperature of atmosphere gas and solution can be a room temperature, and pressure can be atmospheric pressure, and these conditions can suit to change.Dip time for example is about 5 minutes～100 hours, and impregnation can only be carried out once, also can carry out several.
The dyestuff that is adsorbed in porous semiconductor layer 11 like this absorbs luminous energy, produces excitation electron, and performance is sent to these electronics the function of the photosensitizer of porous semiconductor layer 11.That is, form photoelectric conversion layer 31 by absorbing dye in porous semiconductor layer 11.
(carrier transport layer)
Carrier transport layer by can conveying electronic, the material of hole, ion, for example conductive material constitutes.Hole transporting materials such as Polyvinyl carbazole, triphenylamine are arranged particularly, electron transport materials such as tetranitro Fluorenone, electric conductive polymers such as polythiophene, polypyrrole, liquid electrolyte, polyelectrolyte plasma conductor, inorganic P type semiconductor such as cupric iodide, cupric thiocyanate, or the like.
In above-mentioned material, the preferred ion conductor especially preferably contains the electrolytical liquid electrolyte of oxidation-reduction quality.Oxidation-reduction quality electrolyte as such does not have particular restriction, as long as it generally can use in battery, solar cell etc.Can contain I particularly -/ I 3 -Class, Br 2 -/ Br 3 -Class, Fe 2+/ Fe 3+The electrolyte of redox such as class, quinone/hydroquinones kind.For example preferred lithium iodide (LiI), sodium iodide (NaI), KI (KI), calcium iodide (CaI 2) wait metal iodide and iodine (I 2) combination, the combination of tetraethylammonium iodide (TEAI), tetrapropylammonium iodide (TPAI), tetrabutylammonium iodide (TBAI), iodate four own ammonium iodate tetra-allkylammoniums such as (THAI) and iodine, and lithium bromide (LiBr), sodium bromide (NaBr), KBr (KBr), calcium bromide (CaBr 2) wait metal bromide and bromine (Br 2) combination; This wherein, preferred LiI and I 2Combination.
In addition, in carrier transport layer, have as the solvent of liquid electrolyte: carbonats compounds such as propylene carbonate, alcohols such as nitrile compounds such as acetonitrile, ethanol, other also has water, non-proton polar substances etc.This wherein, preferred especially carbonats compound and nitrile compounds.In addition, the above-mentioned solvent that can also be mixed with two or more.
As the additive in the liquid electrolyte, can use normally used tert .-butylpyridine nitrogen-containing aromatic compounds such as (TBP), perhaps dimethyl propyl imidazoles iodide (DMPII), methyl-propyl imidazoles iodide (MPII), ethyl-methyl imidazoles iodide (EMII), ethyl imidazol(e) iodide (EII), hexyl methyl imidazoles iodide imidazole salts such as (HMII), or the like.
In addition, the electrolyte concentration in the liquid electrolyte is preferably in the scope of 0.01～1.5 mol, particularly preferably in the scope of 0.1～0.7 mol.
As polyelectrolyte, can list following solid matter, described solid content can dissolved oxygen original seed also, perhaps can combine with at least a material that constitutes the redox kind.Have particularly: macromolecular compound and crosslinked bodies thereof such as poly(ethylene oxide), PPOX, poly-succinic second diester, poly-beta-propiolactone, polymine, poly-epithio alkane, in the macromolecule functional group of polyphosphazene, polysiloxanes, polyvinyl alcohol, polyacrylic acid, polyalkylene oxide etc., add the compound that forms as the polyether segment of side chain or low polyalkylene oxide structure or their copolymer, or the like; This wherein especially preferably has low polyalkylene oxide structure as the compound of side chain with have the compound of polyether segment as side chain.
Comprise the redox kind in the solid matter in order to make, can adopt for example following method: polymerization is as the monomer methods of macromolecular compound raw material in the presence of the redox kind, solids such as macromolecular compound optionally are dissolved in solvent, add the method for above-mentioned redox kind then, or the like.The content of redox combination can be selected by ionic conductivity as required aptly.
(dividing plate)
In order to prevent photoelectric conversion layer 31 and to contact, can optionally use dividing plate 21 by the electrode 7 that electrode side support is constituted.As dividing plate 21, generally can use polymeric membranes such as polyethylene.The thickness of this polymeric membrane is advisable with 10～50 μ m.
(encapsulant 22)
Photo-electric conversion element of the present invention can also possess encapsulant.As encapsulant 22, there is not particular restriction, as long as it can make that carrier transport layer 4 is unlikely to leak by the sealed photoelectric conversion element.Specifically can use epoxy resin, polyorganosiloxane resin etc.And dividing plate 21 can double as encapsulant 22.And using solid material as carrier transport layer 4, in the time of needn't worrying that carrier transport layer 4 flows out, then encapsulant 22 is also inessential.
(to electrode side support)
As electrode side support is formed electrode 7, it constitutes pair of electrodes with the electrode 3 that is made of conductive supporting member that forms photoelectric conversion layer 31.As electrode 7, extensively adopt the structure that on base material 5, forms conductive layer 6.This conductive layer 6 can be transparent, also can be opaque.As conductive layer 6, can list for example metals such as gold, platinum, silver, copper, aluminium, titanium, tantalum, tungsten; Comprise ITO, SnO 2, transparent conductive material such as ZnO film.Conductive layer 6 can adopt known method to form, and its thickness is advisable with 0.1～5 μ m.And, preferably form catalyst films such as platinum on the surface of conductive layer 6, move with the electric charge that promotes 4 of itself and carrier transport layer.At this moment, the thickness of this catalyst film can be for about 1～1000 μ m.In addition, this catalyst film can double as conductive layer 6.
Can provide photo-electric conversion element by above scheme.Can take photo-electric conversion element of the present invention is linked to each other with external circuit, thereby, provide the dye-sensitized solar cell that uses photo-electric conversion element of the present invention like this to the structure of outside supply capability.
Embodiment
Below, by embodiment and comparative example the present invention is carried out more specific description.But below explanation only is exemplary, can carry out various variations, and the present invention is not subjected to the restriction of these embodiment.
In the present embodiment, at first use the particle diameter Titanium particles suspension identical,, form the different individual layer porous semiconductor layer 11 of mist degree respectively by changing jitter time and the sintering condition in the suspension preparation step with concentration.
In terpineol, add Titanium particles (Teika Co., Ltd. makes, trade name: AMT-600, the about 30nm of particle diameter), add 100g zirconium oxide bead (diameter 2mm) at 40ml solution then, it is dispersed into Titanium particles suspension with the coating oscillator.The time of disperseing with the coating oscillator is 30 minutes, 2 hours, 4 hours, 6 hours and 24 hours.Solution through disperseing is filtered, take out zirconium oxide bead, concentrated filtrate is 15wt% until titanium oxide concentration in evaporator, adds 2 times of ethanol to this solution then, carries out centrifugation with 5000rpm.The Titanium particles that this step is obtained is cleaned with ethanol, adds then ethyl cellulose and terpineol are dissolved in the absolute ethyl alcohol and the solution that makes, and stirs Titanium particles is dispersed in the solution.Under the decompression of 40mbar, the ethanol in 50 ℃ of evaporating liquids has prepared suspension.Adjust concentration, what make suspension finally consists of titanium oxide concentration 10wt%, ethyl cellulose concentration 10wt%, terpineol concentration 64wt%.
Jitter time is that the suspension of 30 minutes, 2 hours, 4 hours, 6 hours and 24 hours is remembered respectively and made suspending liquid A, B, C, D and E.Described suspending liquid A～E is coated respectively on the electrode 3 that is made of conductive supporting member, carry out sintering, thereby formed the individual layer porous semiconductor layer 11 of bed thickness 5 μ m.
As conductive supporting member, used that to be formed with nesa coating be SnO 2The glass plate of film (NHTechno company).This electrical sheet resistance is 10 Ω/.
Adopt silk screen print method as coating process, sintering condition has 9 kinds shown in [1]～[9] of table 1, wherein: the condition that feeds the gas in the sintering furnace is divided into 3 grades of (oxygen 5ml/min, nitrogen 5ml/min, and the gaseous mixture of oxygen 1ml/min and nitrogen 4ml/min), sintering temperature is divided into 3 grades (450 ℃, 480 ℃, 500 ℃).
Table 1
Sintering condition (gas/temperature) 450℃ 480℃ 500℃
(oxygen) 5ml/min [1] [2] [3]
(oxygen)/(nitrogen) (1ml/min)/(4ml/min) [4] [5] [6]
(nitrogen) 5ml/min [7] [8] [9]
(evaluation of bed thickness conversion mist degree)
For 45 kinds of porous semiconductor layers 11 that use above-mentioned 5 kinds of suspending liquid A～E to form by above-mentioned 9 kinds of sintering conditions ([1]～[9]) sintering, adopt the assay method that carries out illumination from the horizontal direction of above-mentioned each layer, measure its mist degree at wavelength 800nm place.In mist degree is measured, used integrating sphere in the magazine of packing into (GPS of Labsphere company series 4 passages) as detector, with optical splitter (Spectroscope company, the M50 type) to xenon lamp (creek pine photoelectricity manufacturing, L2195) light that sends carries out beam split, serves as to measure wavelength with the light of the 800nm that obtains.
For above-mentioned 45 kinds of porous semiconductor layers 11, it is thick to be cut to 10 μ m from semi-conductive vertical plane respectively, as the mist degree test sample.Here, in the cutting of conductive supporting member and porous semiconductor layer 11, use miniature cutter (MARUTO company, MC-201), on the basis of cutting by designated magnitude, use grindstone (MARUTO company, Dialap) and polishing machine (Gatan company, it is thick Model656) to be ground to 10 μ m.
Specimen is thick to be 10 μ m, therefore, by the 5 μ ms identical with the bed thickness of porous semiconductor layer measured value is carried out bed thickness and converts, as the mist degree of porous semiconductor layer 11.Bed thickness converts and is undertaken by aforementioned graphing method.In the present embodiment, can form the different porous semiconductor layers 11 of mist degree in 3～82% scopes.Table 2 is depicted as bed thickness conversion result, the haze results of the specimen when table 3 is depicted as length between section and is 10 μ m.
Below, be example to adopt sintering condition [1] by the porous semiconductor layer 11 that suspending liquid A makes, be described in detail.Adopt sintering condition [1] to make porous semiconductor layer 11a by suspending liquid A by method for printing screen.The thickness of porous semiconductor layer 11a is 5 μ m.Then, adopt sintering condition [1] on porous semiconductor layer 11a, to make porous semiconductor layer 11b by suspending liquid A by method for printing screen.The thickness of porous semiconductor layer 11 (be porous semiconductor layer 11a and porous semiconductor layer 11b thickness and) is 10 μ m.In this case, carry out illumination from the vertical direction of porous semiconductor layer, the mist degree of mensuration is 82%.
Then, adopt sintering condition [1] on porous semiconductor layer 11b, to make porous semiconductor layer 11c by suspending liquid A by method for printing screen.The thickness of porous semiconductor layer 11 (be porous semiconductor layer 11a, porous semiconductor layer 11b and porous semiconductor layer 11c thickness and) is 15 μ m.In this case, carry out illumination from the vertical direction of porous semiconductor layer, the mist degree of mensuration is 83%.
In this case, bed thickness (μ m) with porous semiconductor layer is transverse axis X, with mist degree (%) is longitudinal axis Y mapping, obtain approximate expression Y=(1/5) X+80 by least squqre approximation, can be obtained by this formula: when using suspending liquid A and sintering condition [1] to make the porous semiconductor layer 11a of 5 μ m bed thickness, total mist degree is 81%.In fact, after making porous semiconductor layer 11a, carry out illumination from the vertical direction of porous semiconductor layer, the mist degree of mensuration is 81%.
Table 2
Figure A20068004641000201
Figure A20068004641000211
A=suspension; The b=sintering condition
Table 3
Figure A20068004641000212
A=suspension; The b=sintering condition
For the porous semiconductor layer of in each embodiment of aftermentioned and each comparative example, making 11, adopt said method to calculate bed thickness conversion mist degree, be shown in table 4.
Table 4
Total mist degree of porous semiconductor layer 11 The mist degree of porous semiconductor layer 11a The mist degree of porous semiconductor layer 11b The mist degree of porous semiconductor layer 11c The mist degree of porous semiconductor layer 11d The mist degree of porous semiconductor layer 11e Conversion efficiency (%)
Embodiment 1 81 4 81 - - - 8.0
Embodiment 2 72 3 71 - - - 8.2
Embodiment 3 83 7 83 - - - 8.7
Embodiment 4 85 7 85 - - - 8.8
Embodiment 5 81 4 42 81 - - 9.3
Embodiment 6 81 3 5 81 - - 8.0
Embodiment 7 81 3 29 80 - - 9.0
Embodiment 8 81 4 72 81 - - 8.3
Embodiment 9 81 4 81 81 - - 8.0
Embodiment 10 70 3 29 70 - - 8.8
Embodiment 11 81 29 42 81 - - 7.9
Embodiment 12 81 3 50 81 - - 9.6
Embodiment 13 81 3 51 81 - - 9.2
Embodiment 14 81 3 40 68 81 - 9.5
Embodiment 15 78 10 45 78 - - 9.1
Embodiment 16 83 7 61 83 - - 9.4
Embodiment 17 85 7 65 85 - - 9.6
Embodiment 18 86 7 64 84 - - 9.3
Embodiment 19 72 72 - - - - 8.1
Embodiment 20 83 3 62 66 84 - 9.8
Embodiment 21 87 3 62 66 85 - 9.7
Embodiment 22 84 3 50 62 66 84 9.8
Embodiment 23 67 3 42 62 66 - 9.0
Embodiment 24 85 3 4 62 84 - 9.8
Comparative example 1 52 3 50 - - - 7.2
Comparative example 2 48 4 29 39 - - 7.7
Comparative example 3 55 3 29 51 - - 7.8
Comparative example 4 57 3 28 42 50 - 7.8
For the porous semiconductor layer of in each embodiment of aftermentioned and each comparative example, making 11, adopt from the method for its horizontal direction irradiates light with from the method for its vertical direction irradiates light, carry out mist degree respectively by following step and measure.
(assay method of mist degree)
(employing is measured from the method for the horizontal direction irradiates light of porous semiconductor layer 11)
At first, describe by porous semiconductor layer 11a, porous semiconductor layer b, these 3 layers of situations about constituting of porous semiconductor layer c with regard to porous semiconductor layer 11.
For be formed on the electrode 3 that constitutes by conductive supporting member porous semiconductor layer 11 (here, it constitutes by 3 layers), use miniature cutter (MARUTO company, MC-201) (being cross section 41,42) cuts it along shown in Figure 5, vertical with the semiconductor surface cross section that is spaced apart 300 μ m, made sample as shown in Figure 6.(Gatan company Model623) cuts the cross section of this sample, is about 100 μ m with its skiving to the length between the cross section to use disk grinder.In addition, use polishing machine (Gatan company, Model656) pair cross-section 41 further carries out skiving, makes that the length between the cross section is 10 μ m, with it as specimen 53.
Use mensuration system shown in Figure 7, carry out illumination, measured the mist degree of each layer from the horizontal direction (being the vertical direction in cross section) of semiconductor layer.(manufacturing of creek pine photoelectricity, integrating sphere R928) (GPS of Labsphere company series 4 passages) is as detector 54 to use the band photomultiplier.(light that xenon lamp (creek pine photoelectricity manufacturing, L2195)) sends carries out beam split, serves as to measure wavelength with the light of the 800nm that obtains to light source 51 with wavelength selection system 52 (optical splitter (Spectroscope company make, M50 type)).In addition, (Newport makes, M-FS30-R) to be provided with slit 56.
Make irradiation area narrow by slit 56 to the wide rayed specimen 53 of 3 μ m.Reflecting plate 55 (Labsphere company, Spectralon standard reflection) is arranged at integrating sphere, measures total light penetration.In the mensuration of diffusion transmitance, remove reflecting plate 55, the parallel light 63 that sees through is overflowed, only diffusion is seen through light 64 and measure.Make the position of layer to be measured in the position of peristome of slit 56 and specimen 53 cross sections 41 involutory, obtain the mist degree of porous semiconductor layer 11a, 11b, each layer of porous semiconductor layer 11c.The results are shown in table 5.
(employing is measured from the method for the vertical direction irradiates light of porous semiconductor layer 11)
In embodiment 7,12,14,17,22 described later, adopt following method to carry out illumination from the vertical process of porous semiconductor layer, measured mist degree.
At first, describe by porous semiconductor layer 11a, porous semiconductor layer b, these 3 layers of situations about constituting of porous semiconductor layer c with regard to porous semiconductor layer 11.
Porous semiconductor layer 11 (it is made of multilayer) for being formed on the electrode 3 that is made of conductive supporting member carries out illumination from the vertical direction of porous semiconductor layer 11, has measured total mist degree.In addition, use SEM from cross-section determination thickness.
Then, remove apart from light incident side layer farthest, i.e. porous semiconductor layer 11c with grinder (SCANDIA company 34305)., use SEM from cross-section determination thickness, confirm to have formed porous semiconductor layer 11a, 11b thereafter.
For the porous semiconductor layer that remains (it is made of for these 2 layers porous semiconductor layer 11a, 11b), carry out illumination from the vertical direction of this porous semiconductor layer, measure.Then, remove porous semiconductor layer 11b with grinder.Thereafter, use SEM from cross-section determination thickness, confirm to have formed porous semiconductor layer 11a.Porous semiconductor layer 11a for remaining carries out illumination from its vertical direction, measures its mist degree.
And, when porous semiconductor layer 11 constitutes by 4 layers or 5 layers,, repeat successively to grind the operation of measuring with mist degree from distance light incident side layer farthest by method same as described above, measured the mist degree of each layer.The results are shown in table 6.
(embodiment 1)
Porous semiconductor layer 11 is 2 layers of structure, is followed successively by porous semiconductor layer 11a and porous semiconductor layer 11b from the conductive supporting member side.That is, different with porous semiconductor layer 11a, 11b, 11c shown in Figure 2, formed these 2 layers of porous semiconductor layers that constitutes among the embodiment 1 by porous semiconductor layer 11a, porous semiconductor layer 11b.
At first, adopt silk screen print method coating suspension E (24 hours dispersion liquids) on the conductive supporting member that the glass plate that is produced by as hereinbefore NHTechno company constitutes, pressed sintering condition [1] (5ml/min Oxygen Flow, 450 ℃ of heating down) sintering 1 hour, form porous semiconductor layer 11a, adopt silk screen print method coating suspending liquid A (30 minutes dispersion liquids) then, press sintering condition [1] sintering 1 hour, and formed porous semiconductor layer 11b.
Porous semiconductor layer 11a, 11b bed thickness are respectively 5 μ m, the thick 10 μ m of 2 laminated meters.According to the test result of individual layer, porous semiconductor layer 11a under the described condition, the mist degree of 11b at the 800nm place is respectively 31%, 81%.Use this by the porous semiconductor layer 11 that a plurality of layers constitute, made dye-sensitized solar cell by the following method.
At first, use aforesaid BlackDye, this dyestuff is dissolved in 1: 1 mixed solvent of the acetonitrile and the tert-butyl alcohol, making dye strength is 5 * 10 -4Mol/l adds the deoxycholic acid (Tokyo change into company make) of 20mM again, has prepared the absorption dye solution.
The conductive supporting member that has formed porous semiconductor layer 11 be impregnated in this solution 24 hours, formed photoelectric conversion layer 31.
By the platinum film that constitutes evaporation 300nm on the base material 5 that the glass plate identical with conductive supporting member constitute as conductive layer 6, this be form electrode 7 to electrode side support.
With the thick HIMILAN of 50 μ m (manufacturing of DuPont company) as dividing plate 21, described electrode side support is situated between with the conductive supporting member that is formed with photoelectric conversion layer 31 is piled up by this dividing plate 21, the crack is injected and is served as the electrolyte of carrier transport layer 4 betwixt, with resinous encapsulant 22 its sides of sealing, obtained photo-electric conversion element.This electrolyte has dissolved following substances and has got in acetonitrile (manufacturing of Aldrich company): LiI (0.1M, Aldrich company makes), I 2(0.05M, Aldrich company makes), tert .-butylpyridine (0.5M, Aldrich company makes) and dimethyl propyl imidazoles iodide (0.6M, four countries change into manufacturing).
Use the photo-electric conversion element of making as stated above to make dye-sensitized solar cell of the present invention.With intensity is 100mW/cm 2Light (AM1.5 solar simulator) shine, estimate the photoelectric conversion efficiency of this dye-sensitized solar cell with digital source meter, it is 8.0%.
Then, disassemble this dye-sensitized solar cell, photoelectric conversion layer 31 usefulness acetonitriles are cleaned, remove dyestuff with the sodium hydrate aqueous solution cleaning of 0.01M again, so that mist degree is confirmed.
At first, from the light of the vertical direction incident 800nm of semiconductor layer, measure total mist degree of porous semiconductor layer 11.Total mist degree of porous semiconductor layer 11 is 81%.
Then, press the processing method of the beginning description of the foregoing description, porous semiconductor layer 11 is cut, grinds, make the thick sample of 10 μ m.
Porous semiconductor layer 11a, each layer of 11b are respectively 4%, 81% at the bed thickness conversion mist degree at 800nm place.
(embodiment 2)
Porous semiconductor layer 11a uses suspension E (24 hours dispersion liquids), porous semiconductor layer 11b uses suspension B (2 hours dispersion liquids), all adopt sintering condition [3] (5ml/min Oxygen Flow, 500 ℃ of heating down) to carry out sintering, formed porous semiconductor layer 11.
Porous semiconductor layer 11a, each bed thickness of 11b is respectively 5 μ m, the thick 10 μ m of 2 laminated meters.According to the test result of individual layer, porous semiconductor layer 11a under the described condition, the mist degree of 11b at the 800nm place is respectively 4%, 73%.
In addition, made dye-sensitized solar cell by the method identical with embodiment 1, its photoelectric conversion efficiency is 8.2%.
In addition, measured the total mist degree of porous semiconductor layer 11 at the 800nm place by the mode identical with embodiment 1, it is 72%.
And, having measured porous semiconductor layer 11a by the mode identical with embodiment 1,11b is at the mist degree at 800nm place, and its bed thickness conversion mist degree is respectively 3%, 71%.
(comparative example 1)
Porous semiconductor layer 11a uses suspension E (24 hours dispersion liquids), porous semiconductor layer 11b uses suspension C (4 hours dispersion liquids), all adopt sintering condition [3] (5ml/min Oxygen Flow, 500 ℃ of heating down) to carry out sintering, formed porous semiconductor layer 11.
Porous semiconductor layer 11a, each bed thickness of 11b is respectively 5 μ m, the thick 10 μ m of 2 laminated meters.According to the test result of individual layer, porous semiconductor layer 11a under the described condition, the mist degree of 11b at the 800nm place is respectively 4%, 50%.
In addition, made dye-sensitized solar cell by the method identical with embodiment 1, its photoelectric conversion efficiency is 7.2%.
In addition, measured the total mist degree of porous semiconductor layer 11 at the 800nm place by the mode identical with embodiment 1, it is 52%.
And, measured porous semiconductor layer 11a by the mode identical with embodiment 1, each layer of 11b is at the mist degree at 800nm place, and its bed thickness conversion mist degree is respectively 3%, 50%.
(embodiment 3)
125ml isopropyl titanate (Kishida chemical company makes, purity 99%) is added drop-wise in the 0.1M aqueous solution of nitric acid (manufacturing of Kishida chemical company) of 750mL, makes its hydrolysis, 80 ℃ of heating 8 hours, make sol solution then.In titanium material autoclave in 250 ℃ carry out particle growth 10 hour thereafter.The ultrasonic wave that carried out again 30 minutes disperses, and has made colloidal solution (colloidal solution A), wherein contains the Titanium particles that average primary particle diameter is 15nm.
In evaporator the colloidal solution A that makes being concentrated, is 15wt% until the concentration of titanium oxide, as colloidal solution B, adds 2 times to the ethanol of colloidal solution B, the 5000rpm centrifugation.Clean the Titanium particles that this step makes with ethanol, add then ethyl cellulose and terpineol are dissolved in the absolute ethyl alcohol and the solution that makes, stir Titanium particles is dispersed in the solution.Under 40mbar, the ethanol in 50 ℃ of evaporating liquids has prepared suspension.
Adjust concentration, what make suspension finally consists of titanium oxide concentration 10wt%, ethyl cellulose concentration 10wt%, terpineol concentration 64wt%, and this is suspension F.
Then, in terpineol, add Titanium particles (Teika company, trade name JA-1, Detitanium-ore-type, average primary particle diameter 180nm), add 100g zirconium oxide bead (diameter 2mm) again, carry out 4 hours dispersion treatment with the coating oscillator.Solution through disperseing is filtered, take out zirconium oxide bead, concentrated filtrate is 15wt% until titanium oxide concentration in evaporator, as colloidal solution C.
Then, described colloidal solution C is added in the titanium oxide of colloidal solution B, make it account for 80wt%, add 2 times, carry out centrifugation with 5000rpm to the ethanol of this colloidal solution.The Titanium particles that this step is obtained is cleaned with ethanol, adds then ethyl cellulose and terpineol to be dissolved in the absolute ethyl alcohol and in the solution that makes, and stirs Titanium particles is dispersed in the solution.Under 40mbar, the ethanol in 50 ℃ of evaporating liquids has prepared suspension.
Adjust concentration, what make suspension finally consists of titanium oxide concentration 12wt%, ethyl cellulose concentration 10wt%, terpineol concentration 62wt%, and this is suspension G.
Porous semiconductor layer 11a uses suspension F, and porous semiconductor layer 11b uses suspension G, all adopts sintering condition [3] (5ml/min Oxygen Flow, 500 ℃ of heating down) to carry out sintering, has formed porous semiconductor layer 11.Porous semiconductor layer 11a, each bed thickness of 11b is respectively 5 μ m, the thick 10 μ m of 2 laminated meters.
In addition, made dye-sensitized solar cell by the method identical with embodiment 1, its photoelectric conversion efficiency is 8.7%.
In addition, measured the total mist degree of porous semiconductor layer 11 at the 800nm place by the mode identical with embodiment 1, it is 83%.
And, measured porous semiconductor layer 11a by the mode identical with embodiment 1, each layer of 11b is at the mist degree at 800nm place, and its bed thickness conversion mist degree is respectively 7%, 83%.
(embodiment 4)
Made suspension H by the method for preparing embodiment 3 suspension G, different is: be that the Titanium particles of 350nm (Nano-clean Science company) has replaced the Titanium particles among the preparation method of embodiment 3 suspension G with the average primary particle diameter.
Porous semiconductor layer 11a uses suspension F, and porous semiconductor layer 11b uses suspension H, all adopts sintering condition [3] (5ml/min Oxygen Flow, 500 ℃ of heating down) to carry out sintering, has formed porous semiconductor layer 11.Porous semiconductor layer 11a, each bed thickness of 11b is respectively 5 μ m, the thick 10 μ m of 2 laminated meters.
In addition, made dye-sensitized solar cell by the method identical with embodiment 1, its photoelectric conversion efficiency is 8.8%.
In addition, measured the total mist degree of porous semiconductor layer 11 at the 800nm place by the mode identical with embodiment 1, it is 85%.
And, measured porous semiconductor layer 11a by the mode identical with embodiment 1, each layer of 11b is at the mist degree at 800nm place, and its bed thickness conversion mist degree is respectively 7%, 85%.
In addition, carried out the cleaning with photoelectric conversion layer 31 of disassembling of dye sensitization battery by the mode identical with embodiment 1, thereafter remove porous semiconductor layer 11b with grinder, the porous semiconductor layer 11a that mensuration remains is at the mist degree at 800nm place, and this mist degree is 7%.Thereby, total mist degree of 2 layers porous semiconductor layer 11 can be considered as the mist degree of the 2nd layer porous semiconductor layer 11b.That is, adopt such assay method also can measure porous semiconductor layer 11a, the mist degree of each layer of porous semiconductor layer 11b.
(embodiment 5)
Porous semiconductor layer 11 adopts 3-tier architecture shown in Figure 2, is respectively porous semiconductor layer 11a, 11b, 11c from conductive supporting member one side.
Adopt silk screen print method coating suspension E (24 hours dispersion liquids) on the conductive supporting member that the glass plate of being produced by as hereinbefore NHTechno company constitutes, press sintering condition [1] (5ml/min Oxygen Flow, 450 ℃ of heating down) sintering is 1 hour, form porous semiconductor layer 11a, adopt silk screen print method coating suspension C (4 hours dispersion liquids) then, pressed sintering condition [1] sintering 1 hour, formed porous semiconductor layer porous semiconductor layer 11b, silk screen print method coating suspending liquid A (30 minutes dispersion liquids) is adopted in the back again, press sintering condition [1] sintering 1 hour, and formed porous semiconductor layer 11c.
Porous semiconductor layer 11a, 11b, each bed thickness of 11c is respectively 5 μ m, the thick 15 μ m of 3 laminated meters.According to the test result of individual layer, porous semiconductor layer 11a under the described condition, 11b, the mist degree of 11c at the 800nm place is respectively 3%, 40%, 81%.
In addition, make dye-sensitized solar cell by the method identical with embodiment 1, its photoelectric conversion efficiency is 9.3%.
In addition, measured the total mist degree of porous semiconductor layer 11 at the 800nm place by the mode identical with embodiment 1, it is 81%.
And, having measured porous semiconductor layer 11a by the mode identical with embodiment 1,11b, each layer of 11c are at the mist degree at 800nm place, and its bed thickness conversion mist degree is respectively 4%, 42%, 81%.
(embodiment 6)
Porous semiconductor layer 11a, 11b uses suspension E (24 hours dispersion liquids), porous semiconductor layer 11c uses suspending liquid A (30 minutes dispersion liquids), all adopts sintering condition [1] (5ml/min Oxygen Flow, 450 ℃ of heating down) to carry out sintering, has formed porous semiconductor layer 11.
Porous semiconductor layer 11a, 11b, each bed thickness of 11c is respectively 5 μ m, the thick 15 μ m of 3 laminated meters.According to the test result of individual layer, porous semiconductor layer 11a under the described condition, 11b, the mist degree of 11c at the 800nm place is respectively 3%, 3%, 81%.
In addition, made dye-sensitized solar cell by the method identical with embodiment 1, its photoelectric conversion efficiency is 8.0%.
In addition, measure the total mist degree of porous semiconductor layer 11 at the 800nm place by the mode identical with embodiment 1, it is 81%.
And, having measured porous semiconductor layer 11a by the mode identical with embodiment 1,11b, each layer of 11c are at the mist degree at 800nm place, and its bed thickness conversion mist degree is respectively 3%, 5%, 81%.
(embodiment 7)
Porous semiconductor layer 11a uses suspension E (24 hours dispersion liquids), porous semiconductor layer 11b uses suspension D (6 hours dispersion liquids), porous semiconductor layer 11c uses suspending liquid A (30 minutes dispersion liquids), all adopt sintering condition [1] (5ml/min Oxygen Flow, 450 ℃ of heating down) to carry out sintering, formed porous semiconductor layer 11.
Porous semiconductor layer 11a, 11b, each bed thickness of 11c is respectively 5 μ m, the thick 15 μ m of 3 laminated meters.According to the test result of individual layer, porous semiconductor layer 11a under the described condition, 11b, the mist degree of 11c at the 800nm place is respectively 3%, 28%, 81%.
In addition, made dye-sensitized solar cell by the method identical with embodiment 1, its photoelectric conversion efficiency is 9.0%.
In addition, measured the total mist degree of porous semiconductor layer 11 at the 800nm place by the mode identical with embodiment 1, it is 81%.
And, having measured porous semiconductor layer 11a by the mode identical with embodiment 1,11b, each layer of 11c are at the mist degree at 800nm place, and its bed thickness conversion mist degree is respectively 3%, 29%, 80%.
(embodiment 8)
Porous semiconductor layer 11a uses suspension E (24 hours dispersion liquids), porous semiconductor layer 11b uses suspension B (2 hours dispersion liquids), porous semiconductor layer 11c uses suspending liquid A (30 minutes dispersion liquids), all adopt sintering condition [1] (5ml/min Oxygen Flow, 450 ℃ of heating down) to carry out sintering, formed porous semiconductor layer 11.
Porous semiconductor layer 11a, 11b, 11c bed thickness are respectively 5 μ m, the thick 15 μ m of 3 laminated meters.According to the test result of individual layer, porous semiconductor layer 11a under the described condition, 11b, the mist degree of 11c at the 800nm place is respectively 3%, 72%, 81%.
In addition, made dye-sensitized solar cell by the method identical with embodiment 1, its photoelectric conversion efficiency is 8.3%.
In addition, measured the total mist degree of porous semiconductor layer 11 at the 800nm place by the mode identical with embodiment 1, it is 81%.
And, having measured porous semiconductor layer 11a by the mode identical with embodiment 1,11b, each layer of 11c are at the mist degree at 800nm place, and its bed thickness conversion mist degree is respectively 4%, 72%, 81%.
(embodiment 9)
Porous semiconductor layer 11a uses suspension E (24 hours dispersion liquids), porous semiconductor layer 11b and porous semiconductor layer 11c use suspending liquid A (30 minutes dispersion liquids), all adopt sintering condition [1] (5ml/min Oxygen Flow, 450 ℃ of heating down) to carry out sintering, formed porous semiconductor layer 11.
Porous semiconductor layer 11a, 11b, 11c bed thickness are respectively 5 μ m, the thick 15 μ m of 3 laminated meters.According to the test result of individual layer, porous semiconductor layer 11a under the described condition, 11b, the mist degree of 11c at the 800nm place is respectively 3%, 81%, 81%.
In addition, made dye-sensitized solar cell by the method identical with embodiment 1, its photoelectric conversion efficiency is 8.0%.
In addition, measured the total mist degree of porous semiconductor layer 11 at the 800nm place by the mode identical with embodiment 1, it is 81%.
And, having measured porous semiconductor layer 11a by the mode identical with embodiment 1,11b, each layer of 11c are at the mist degree at 800nm place, and its bed thickness conversion mist degree is respectively 4%, 81%, 81%.
(embodiment 10)
Porous semiconductor layer 11a uses suspension E (24 hours dispersion liquids), porous semiconductor layer 11b uses suspension D (6 hours dispersion liquids), porous semiconductor layer 11c uses suspension B (2 hours dispersion liquids), all adopt sintering condition [1] (5ml/min Oxygen Flow, 450 ℃ of heating down) to carry out sintering, formed porous semiconductor layer 11.
Porous semiconductor layer 11a, 11b, each bed thickness of 11c is respectively 5 μ m, the thick 15 μ m of 3 laminated meters.According to the test result of individual layer, porous semiconductor layer 11a under the described condition, 11b, the mist degree of 11c at the 800nm place is respectively 3%, 28%, 72%.
In addition, made dye-sensitized solar cell by the method identical with embodiment 1, its photoelectric conversion efficiency is 8.8%.
In addition, measured the total mist degree of porous semiconductor layer 11 at the 800nm place by the mode identical with embodiment 1, it is 70%.
And, having measured porous semiconductor layer 11a by the mode identical with embodiment 1,11b, each layer of 11c are at the mist degree at 800nm place, and its bed thickness conversion mist degree is respectively 3%, 29%, 70%.
(comparative example 2)
Porous semiconductor layer 11a uses suspension E (24 hours dispersion liquids), porous semiconductor layer 11b uses suspension D (6 hours dispersion liquids), porous semiconductor layer 11c uses suspension C (4 hours dispersion liquids), all adopt sintering condition [1] (5ml/min Oxygen Flow, 450 ℃ of heating down) to carry out sintering, formed porous semiconductor layer 11.
Porous semiconductor layer 11a, 11b, each bed thickness of 11c is respectively 5 μ m, the thick 15 μ m of 3 laminated meters.According to the test result of individual layer, porous semiconductor layer 11a under the described condition, 11b, the mist degree of 11c at the 800nm place is respectively 3%, 28%, 40%.
In addition, made dye-sensitized solar cell by the method identical with embodiment 1, its photoelectric conversion efficiency is 7.7%.
In addition, measured the total mist degree of porous semiconductor layer 11 at the 800nm place by the mode identical with embodiment 1, it is 48%.
And, having measured porous semiconductor layer 11a by the mode identical with embodiment 1,11b, 11c are at the mist degree at 800nm place, and its bed thickness conversion mist degree is respectively 4%, 29%, 39%.
(embodiment 11)
Porous semiconductor layer 11a uses suspension D (6 hours dispersion liquids), porous semiconductor layer 11b uses suspension C (4 hours dispersion liquids), porous semiconductor layer 11c uses suspending liquid A (30 minutes dispersion liquids), all adopt sintering condition [1] (5ml/min Oxygen Flow, 450 ℃ of heating down) to carry out sintering, formed porous semiconductor layer 11.
Porous semiconductor layer 11a, 11b, each bed thickness of 11c is respectively 5 μ m, the thick 15 μ m of 3 laminated meters.According to the test result of individual layer, porous semiconductor layer 11a under the described condition, 11b, the mist degree of 11c at the 800nm place is respectively 28%, 40%, 81%.
In addition, made dye-sensitized solar cell by the method identical with embodiment 1, its photoelectric conversion efficiency is 7.9%.
In addition, measured the total mist degree of porous semiconductor layer 11 at the 800nm place by the mode identical with embodiment 1, it is 81%.
And, having measured porous semiconductor layer 11a by the mode identical with embodiment 1,11b, each layer of 11c are at the mist degree at 800nm place, and its bed thickness conversion mist degree is respectively 29%, 42%, 81%.
(embodiment 12)
Porous semiconductor layer 11a uses suspension E (24 hours dispersion liquids), porous semiconductor layer 11b uses suspension C (4 hours dispersion liquids), porous semiconductor layer 11c uses suspending liquid A (30 minutes dispersion liquids), all adopt sintering condition [3] (5ml/min Oxygen Flow, 500 ℃ of heating down) to carry out sintering, formed porous semiconductor layer 11.
Porous semiconductor layer 11a, 11b, each bed thickness of 11c is respectively 5 μ m, the thick 15 μ m of 3 laminated meters.According to the test result of individual layer, porous semiconductor layer 11a under the described condition, 11b, the mist degree of 11c at the 800nm place is respectively 4%, 50%, 80%.
In addition, made dye-sensitized solar cell by the method identical with embodiment 1, its photoelectric conversion efficiency is 9.6%.
In addition, measured the total mist degree of porous semiconductor layer 11 at the 800nm place by the mode identical with embodiment 1, it is 81%.
And, having measured porous semiconductor layer 11a by the mode identical with embodiment 1,11b, each layer of 11c are at the mist degree at 800nm place, and its bed thickness conversion mist degree is respectively 3%, 50%, 81%.
(embodiment 13)
Porous semiconductor layer 11a uses suspension E (24 hours dispersion liquids), porous semiconductor layer 11b uses suspension C (4 hours dispersion liquids), porous semiconductor layer 11c uses suspending liquid A (30 minutes dispersion liquids), all adopt sintering condition [6] (1ml/min oxygen and 4ml/min stream of nitrogen gas, 500 ℃ of heating down) to carry out sintering, formed porous semiconductor layer 11.
Porous semiconductor layer 11a, 11b, each bed thickness of 11c is respectively 5 μ m, the thick 15 μ m of 3 laminated meters.According to the test result of individual layer, porous semiconductor layer 11a under the described condition, 11b, the mist degree of 11c at the 800nm place is respectively 5%, 51%, 81%.
In addition, made dye-sensitized solar cell by the method identical with embodiment 1, its photoelectric conversion efficiency is 9.2%.
In addition, measured the total mist degree of porous semiconductor layer 11 at the 800nm place by the mode identical with embodiment 1, it is 81%.
And, having measured porous semiconductor layer 11a by the mode identical with embodiment 1,11b, each layer of 11c are at the mist degree at 800nm place, and its bed thickness conversion mist degree is respectively 3%, 51%, 81%.
(embodiment 14)
Porous semiconductor layer 11 adopts 4 layers of structure shown in Figure 3, is respectively porous semiconductor layer 11a, 11b, 11c, 11d from the conductive supporting member side.
Porous semiconductor layer 11a uses suspension E (24 hours dispersion liquids), porous semiconductor layer 11b uses suspension C (4 hours dispersion liquids), porous semiconductor layer 11c uses suspension B (2 hours dispersion liquids), porous semiconductor layer 11d uses suspending liquid A (30 minutes dispersion liquids), all adopt sintering condition [1] (5ml/min Oxygen Flow, 450 ℃ of heating down) to carry out sintering, formed porous semiconductor layer 11.
Porous semiconductor layer 11a, 11b, 11c, 11d bed thickness are respectively 5 μ m, the thick 20 μ m of 4 laminated meters.According to the test result of individual layer, porous semiconductor layer 11a under the described condition, 11b, 11c, the mist degree of 11d at the 800nm place is respectively 3%, 40%, 72%, 81%.
In addition, made dye-sensitized solar cell by the method identical with embodiment 1, its photoelectric conversion efficiency is 9.5%.
In addition, measured the total mist degree of porous semiconductor layer 11 at the 800nm place by the mode identical with embodiment 1, it is 81%.
And, having measured porous semiconductor layer 11a by the mode identical with embodiment 1,11b, 11c, 11d are at the mist degree at 800nm place, and its bed thickness conversion mist degree is respectively 3%, 40%, 68%, 81%.
(embodiment 15)
Press preparation method's supending of suspension C and suspension E, different is: as the Titanium particles that is used to form suspension, used AMT-600 (the about 30nm of the particle diameter) 50wt% of Teika company and the mixture of JA-1 (the about 180nm of particle diameter) 50wt%; Suspension C2 (disperseing 4 hours) and suspension E2 (disperseing 24 hours) have been made respectively with the coating oscillator with the coating oscillator.
Porous semiconductor layer 11a uses suspension E2 (24 hours dispersion liquids of stuff and other stuff), porous semiconductor layer 11b uses suspension C (4 hours dispersion liquids), porous semiconductor layer 11c uses suspension C2 (4 hours dispersion liquids of stuff and other stuff), all adopt sintering condition [1] (5ml/min Oxygen Flow, 450 ℃ of heating down) to carry out sintering, formed porous semiconductor layer 11. Porous semiconductor layer 11a, 11b, each bed thickness of 11c is respectively 5 μ m, the thick 15 μ m of 3 laminated meters.
In addition, made dye-sensitized solar cell by the method identical with embodiment 1, its photoelectric conversion efficiency is 9.1%.
In addition, measured the total mist degree of porous semiconductor layer 11 at the 800nm place by the mode identical with embodiment 1, it is 78%.
And, having measured porous semiconductor layer 11a by the mode identical with embodiment 1,11b, each layer of 11c are at the mist degree at 800nm place, and its bed thickness conversion mist degree is respectively 10%, 45%, 78%.
(embodiment 16)
Preparation method by suspension G has prepared suspension, and different is: add Titanium particles (Teika company, trade name JA-1, Detitanium-ore-type, average primary particle diameter 180nm) and the stirring of 10wt% with respect to described colloidal solution B.
Adjust concentration, make finally to consist of titanium oxide concentration 12wt%, ethyl cellulose concentration 10wt%, terpineol concentration 62wt%, this is suspension I.
Porous semiconductor layer 11a uses suspension F, and porous semiconductor layer 11b uses suspension I, and porous semiconductor layer 11c uses suspension G, all adopts sintering condition [3] (5ml/min Oxygen Flow, 500 ℃ of heating down) to carry out sintering, has formed porous semiconductor layer 11. Porous semiconductor layer 11a, 11b, each bed thickness of 11c is respectively 5 μ m, the thick 15 μ m of 3 laminated meters.
In addition, made dye-sensitized solar cell by the method identical with embodiment 1, its photoelectric conversion efficiency is 9.4%.
In addition, measured the total mist degree of porous semiconductor layer 11 at the 800nm place by the mode identical with embodiment 1, it is 83%.
And, having measured porous semiconductor layer 11a by the mode identical with embodiment 1,11b, each layer of 11c are at the mist degree at 800nm place, and its bed thickness conversion mist degree is respectively 7%, 61%, 83%.
(embodiment 17)
Preparation method by the suspension I of embodiment 16 has prepared suspension J, and different is: use the Titanium particles (Nano-clean Science company) of average primary particle diameter 350nm to replace JA-1, obtained suspension J.
Porous semiconductor layer 11a uses suspension F, and porous semiconductor layer 11b uses suspension J, and porous semiconductor layer 11c uses suspension H, all adopt sintering condition [3] (5ml/min Oxygen Flow, 500 ℃ of heating down) to carry out sintering, formed porous semiconductor layer 11a, 11b, 11c.Each bed thickness is respectively 5 μ m, the thick 15 μ m of 3 laminated meters.
In addition, made dye-sensitized solar cell by the method identical with embodiment 1, its photoelectric conversion efficiency is 9.6%.
In addition, measured the total mist degree of porous semiconductor layer 11 at the 800nm place by the mode identical with embodiment 1, it is 85%.
And, having measured porous semiconductor layer 11a by the mode identical with embodiment 1,11b, each layer of 11c are at the mist degree at 800nm place, and its bed thickness conversion mist degree is respectively 7%, 65%, 85%.
(embodiment 18)
Prepared the colloidal solution of the Titanium particles that contains average primary particle diameter 350nm by the method for implementing 3, different is: in the preparation process of embodiment 3 suspension F, be 250 ℃, 96 hours with the condition setting of particle growth in the titanium system autoclave.
Then, use this colloidal solution, prepared suspension by the preparation process of embodiment 3 suspension F.Adjust concentration, make finally to consist of titanium oxide concentration 10wt%, ethyl cellulose concentration 10wt%, terpineol concentration 64wt%, this is suspension K.
Suspension F is mixed by weight 9: 1 with suspension K, make suspension L.
Porous semiconductor layer 11a uses suspension F, and porous semiconductor layer 11b uses suspension L, and porous semiconductor layer 11c uses suspension K, all adopts sintering condition [3] (5ml/min Oxygen Flow, 500 ℃ of heating down) to carry out sintering, has formed porous semiconductor layer 11. Porous semiconductor layer 11a, 11b, each bed thickness of 11c is respectively 5 μ m, the thick 15 μ m of 3 laminated meters.
In addition, made dye-sensitized solar cell by the method identical with embodiment 1, its photoelectric conversion efficiency is 9.3%.
In addition, measured the total mist degree of porous semiconductor layer 11 at the 800nm place by the mode identical with embodiment 1, it is 86%.
And, having measured porous semiconductor layer 11a by the mode identical with embodiment 1,11b, each layer of 11c are at the mist degree at 800nm place, and its bed thickness conversion mist degree is respectively 7%, 64%, 84%.
(embodiment 19)
Adopt silk screen print method that the suspension I for preparing among the embodiment 16 is coated on the conductive supporting member, adopt sintering condition [3] (5ml/min Oxygen Flow, 500 ℃ of heating down) to carry out sintering, formed porous semiconductor layer 11.Bed thickness is 15 μ m.
In addition, made dye-sensitized solar cell by the method identical with embodiment 1, its photoelectric conversion efficiency is 8.1%.
In addition, measured the total mist degree of porous semiconductor layer 11 at the 800nm place by the mode identical with embodiment 1, it is 72%.
And, measured the mist degree of porous semiconductor layer 11 by the mode (but the thick 15 μ m of sample) identical at the 800nm place with embodiment 1, its mist degree is 72%.
(embodiment 20)
Porous semiconductor layer is 4 layers of structure, is respectively porous semiconductor layer 11a, 11b, 11c, 11d from the conductive supporting member side.
Porous semiconductor layer 11a uses suspension F, porous semiconductor layer 11b uses suspension I, porous semiconductor layer 11c uses suspension J, porous semiconductor layer 11d uses suspension K, all adopt sintering condition [1] (5ml/min Oxygen Flow, 450 ℃ of heating down) to carry out sintering, formed porous semiconductor layer 11. Porous semiconductor layer 11a, 11b, 11c, 11d bed thickness are respectively 5 μ m, the thick 20 μ m of 4 laminated meters.
In addition, made dye-sensitized solar cell by the method identical with embodiment 1, its photoelectric conversion efficiency is 9.8%.
In addition, measured the total mist degree of porous semiconductor layer 11 at the 800nm place by the mode identical with embodiment 1, it is 83%.
And, having measured porous semiconductor layer 11a by the mode identical with embodiment 1,11b, 11c, each layer of 11d are at the mist degree at 800nm place, and its bed thickness conversion mist degree is respectively 3%, 62%, 66%, 84%.
(embodiment 21)
Porous semiconductor layer 11a uses suspension F, porous semiconductor layer 11b uses suspension I, porous semiconductor layer 11c uses suspension J, porous semiconductor layer 11d uses suspension H, all adopt sintering condition [1] (5ml/min Oxygen Flow, 450 ℃ of heating down) to carry out sintering, formed porous semiconductor layer 11. Porous semiconductor layer 11a, 11b, 11c, each bed thickness of 11d is respectively 5 μ m, the thick 20 μ m of 4 laminated meters.
In addition, made dye-sensitized solar cell by the method identical with embodiment 1, its photoelectric conversion efficiency is 9.7%.
In addition, measured the total mist degree of porous semiconductor layer 11 at the 800nm place by the mode identical with embodiment 1, it is 87%.
And, having measured porous semiconductor layer 11a by the mode identical with embodiment 1,11b, 11c, each layer of 11d are at the mist degree at 800nm place, and its bed thickness conversion mist degree is respectively 3%, 62%, 66%, 85%.
(embodiment 22)
Porous semiconductor layer is 5 layers of structure shown in Figure 4, is respectively porous semiconductor layer 11a, 11b, 11c, 11d, 11e from the conductive supporting member side.
Porous semiconductor layer 11a uses suspension F, porous semiconductor layer 11b uses suspension C, porous semiconductor layer 11c uses suspension I, porous semiconductor layer 11d uses suspension J, porous semiconductor layer 11e uses suspension K, all adopt sintering condition [1] (5ml/min Oxygen Flow, 450 ℃ of heating down) to carry out sintering, formed porous semiconductor layer 11. Porous semiconductor layer 11a, 11b, 11c, 11d, each bed thickness of 11e is respectively 5 μ m, the thick 25 μ m of 5 laminated meters.
In addition, made dye-sensitized solar cell by the method identical with embodiment 1, its photoelectric conversion efficiency is 9.8%.
In addition, measured the total mist degree of porous semiconductor layer 11 at the 800nm place by the mode identical with embodiment 1, it is 84%.
And, having measured porous semiconductor layer 11a by the mode identical with embodiment 1,11b, 11c, 11d, each layer of 11e are at the mist degree at 800nm place, and its bed thickness conversion mist degree is respectively 3%, 50%, 62%, 66%, 84%.
(embodiment 23)
Porous semiconductor layer 11 is 4 layers of structure, is respectively porous semiconductor layer 11a, 11b, 11c, 11d from the conductive supporting member side.
Porous semiconductor layer 11a uses suspension F, porous semiconductor layer 11b uses suspension C, porous semiconductor layer 11c uses suspension I, porous semiconductor layer 11d uses suspension J, all adopt sintering condition [3] (5ml/min Oxygen Flow, 500 ℃ of heating down) to carry out sintering, formed porous semiconductor layer 11. Porous semiconductor layer 11a, 11b, 11c, each bed thickness of 11d is respectively 5 μ m, the thick 20 μ m of 4 laminated meters.
In addition, made dye-sensitized solar cell by the method identical with embodiment 1, its photoelectric conversion efficiency is 9.0%.
In addition, measured the total mist degree of porous semiconductor layer 11 at the 800nm place by the mode identical with embodiment 1, it is 67%.
And, having measured porous semiconductor layer 11a by the mode identical with embodiment 1,11b, 11c, each layer of 11d are at the mist degree at 800nm place, and its bed thickness conversion mist degree is respectively 3%, 42%, 62%, 66%.
(comparative example 3)
Porous semiconductor layer is a 3-tier architecture, is respectively porous semiconductor layer 11a, 11b, 11c from the conductive supporting member side.
Porous semiconductor layer 11a uses suspension E (24 hours dispersion liquids), and porous semiconductor layer 11b uses suspension D (6 hours dispersion liquids), all adopts sintering condition [1] (5ml/min Oxygen Flow, 450 ℃ of heating down) to carry out sintering; Porous semiconductor layer 11c uses suspension C (4 hours dispersion liquids), adopts sintering condition [9] (5ml/min nitrogen current, 500 ℃ of heating down) to carry out sintering; Formed porous semiconductor layer 11.
Porous semiconductor layer 11a, 11b, each bed thickness of 11c is respectively 5 μ m, the thick 15 μ m of 3 laminated meters.According to the test result of individual layer, porous semiconductor layer 11a under the described condition, 11b, the mist degree of 11c at the 800nm place is respectively 3%, 28%, 52%.
In addition, made dye-sensitized solar cell by the method identical with embodiment 1, its photoelectric conversion efficiency is 7.8%.
In addition, measured the total mist degree of porous semiconductor layer 11 at the 800nm place by the mode identical with embodiment 1, it is 55%.
And, having measured porous semiconductor layer 11a by the mode identical with embodiment 1,11b, 11c are at the mist degree at 800nm place, and its bed thickness conversion mist degree is respectively 3%, 29%, 51%.
(comparative example 4)
Porous semiconductor layer is 4 layers of structure, is respectively porous semiconductor layer 11a, 11b, 11c, 11d from the conductive supporting member side.
Porous semiconductor layer 11a uses suspension E, and porous semiconductor layer 11b uses suspension D, all adopts sintering condition [3] (5ml/min Oxygen Flow, 500 ℃ of heating down) to carry out sintering; Porous semiconductor layer 11c uses suspension C, adopts sintering condition [1] (5ml/min Oxygen Flow, 450 ℃ of heating down) to carry out sintering; Porous semiconductor layer 11d uses suspension C, adopts sintering condition [3] (5ml/min Oxygen Flow, 500 ℃ of heating down) to carry out sintering, has formed porous semiconductor layer 11. Porous semiconductor layer 11a, 11b, 11c, each bed thickness of 11d is respectively 5 μ m, the thick 20 μ m of 4 laminated meters.
In addition, made dye-sensitized solar cell by the method identical with embodiment 1, its photoelectric conversion efficiency is 7.8%.
In addition, measured the total mist degree of porous semiconductor layer 11 at the 800nm place by the mode identical with embodiment 1, it is 57%.
And, having measured porous semiconductor layer 11a by the mode identical with embodiment 1,11b, 11c, each layer of 11d are at the mist degree at 800nm place, and its bed thickness conversion mist degree is respectively 3%, 28%, 42%, 50%.
(embodiment 24)
Porous semiconductor layer is 4 layers of structure, is respectively porous semiconductor layer 11a, 11b, 11c, 11d from the conductive supporting member side.
Porous semiconductor layer 11a uses suspension F, and porous semiconductor layer 11b uses suspension F, all adopts sintering condition [3] (5ml/min Oxygen Flow, 500 ℃ of heating down) to carry out sintering; Porous semiconductor layer 11c uses suspension I, adopts sintering condition [3] (5ml/min Oxygen Flow, 500 ℃ of heating down) to carry out sintering; Porous semiconductor layer 11d uses suspension K, adopts sintering condition [3] (5ml/min Oxygen Flow, 500 ℃ of heating down) to carry out sintering; Formed porous semiconductor layer 11. Porous semiconductor layer 11a, 11b, 11c, each bed thickness of 11d is respectively 5 μ m, the thick 20 μ m of 4 laminated meters.
In addition, made dye-sensitized solar cell by the method identical with embodiment 1, its photoelectric conversion efficiency is 9.8%.
In addition, measured the total mist degree of porous semiconductor layer 11 at the 800nm place by the mode identical with embodiment 1, it is 85%.
And, having measured porous semiconductor layer 11a by the mode identical with embodiment 1,11b, 11c, each layer of 11d are at the mist degree at 800nm place, and its bed thickness conversion mist degree is respectively 3%, 4%, 62%, 84%.
[table 5]
The mist degree of porous semiconductor layer 11a The mist degree of porous semiconductor layer 11b The mist degree of porous semiconductor layer 11c The mist degree of porous semiconductor layer 11d The mist degree of porous semiconductor layer 11e
Embodiment
1 5 82 - - -
Embodiment 2 4 72 - - -
Embodiment 3 8 84 - - -
Embodiment 4 8 86 - - -
Embodiment 5 5 53 82 - -
Embodiment 6 4 6 82 - -
Embodiment 7 4 43 81 - -
Embodiment 8 5 74 82 - -
Embodiment 9 5 82 82 - -
Embodiment 10 4 43 72 - -
Embodiment 11 42 53 82 - -
Embodiment 12 4 56 82 - -
Embodiment 13 4 57 82 - -
Embodiment 14 4 51 69 82 -
Embodiment 15 10 55 79 - -
Embodiment 16 8 66 84 - -
Embodiment 17 8 67 86 - -
Embodiment 18 8 66 85 - -
Embodiment 19 66 - - - -
Embodiment 20 4 64 69 85 -
Embodiment 21 4 65 69 86 -
Embodiment 22 4 59 64 69 85
Embodiment 23 5 53 66 69 -
Embodiment 24 4 5 65 85 -
Comparative example 1 4 56 - - -
Comparative example 2 5 43 50 - -
Comparative example 3 5 43 58 - -
Comparative example 4 4 43 50 59 -
Table 6
The mist degree of porous semiconductor layer 11a This mist degree of 2 layers of porous semiconductor layer 11a, 11b Porous semiconductor layer 11a, 11b, this mist degree of 3 layers of 11c Porous semiconductor layer 11a, 11b, this mist degree of 4 layers of 11c, 11d Porous semiconductor layer 11a, 11b, 11c, 11d, this mist degree of 5 layers of 11e
Embodiment
7 3 30 81 - -
Embodiment 12 3 52 81 - -
Embodiment 14 3 41 69 81 -
Embodiment 17 7 66 85 - -
Embodiment 22 3 52 63 67 84
(summary of embodiment 1～24)
Following content that hence one can see that.
1. with regard to the photo-electric conversion element with the porous semiconductor layer 11 that has adsorbed dyestuff, in order to obtain high-photoelectric transformation efficiency, (preferred 780～900nm) mist degree is important to regulation porous semiconductor layer 11 in the near infrared region.
2. from above-mentioned 1 and the result (for example embodiment 14,23 etc.) of embodiment, particularly when total mist degree of near infrared region be more than 60% and below 95% when (preferred more than 70% and below 95%), can obtain the high photo-electric conversion element of photoelectric conversion efficiency.Here.Maximum 95% is to stipulate according to the maximum of the mist degree that obtains by experiment in an embodiment.
3. in order light to be enclosed in the porous semiconductor layer 11 effectively, preferably porous semiconductor layer 11 is made of the different a plurality of porous semiconductor layers of mist degree, and increases (referring to two of working of an invention mode: about mist degree) successively from the light incident side mist degree of light.Result from above understanding and above-mentioned 2, with regard to the porous semiconductor layer 11 that constitutes by a plurality of layers, if apart from the mist degree of light incident side porous semiconductor layer farthest in the near infrared region is (preferred more than 70% and below 95%) more than 60% and below 95%, then can obtain the high photo-electric conversion element of photoelectric conversion efficiency.This point is further confirmed by experiment.
4. from the result of for example embodiment 11 and embodiment 15,, then can obtain high photoelectric conversion efficiency if the mist degree of porous semiconductor layer 11a in the near infrared region nearest apart from light incident side is 10%.Therefore, in the porous semiconductor layer 11 that constitutes by a plurality of layer,, can list more than 1% and less than 11% as the preferable range of the nearest porous semiconductor layer of distance light incident side at the mist degree of near infrared region.This minimum value 1% be the experiment value when measuring total mist degree stipulate ((for example evaporation has SnO because of general conductive supporting member 2The glass plate of film) haze value is about 1%).
5. according to above-mentioned 3 and 4, when porous semiconductor layer 11 constitutes by 3 layers, preferably: porous semiconductor layer 11a the mist degree near infrared region nearest apart from light incident side is more than 1% and less than 11%, is (more preferably more than 70% and below 95%) more than 60% and below 95% apart from the mist degree of light incident side porous semiconductor layer 11c farthest in the near infrared region.
6. the same with above-mentioned 5, when porous semiconductor layer 11 constitutes by 4 layers, preferably: porous semiconductor layer 11a the mist degree near infrared region nearest apart from light incident side is more than 1% and less than 11%, is (more preferably more than 70% and below 95%) more than 60% and below 95% apart from the mist degree of light incident side porous semiconductor layer 11d farthest in the near infrared region.
7. the same with above-mentioned 5 and 6, when porous semiconductor layer 11 constitutes by 5 layers, preferably: porous semiconductor layer 11a the mist degree near infrared region nearest apart from light incident side is more than 1% and less than 11%, is (more preferably more than 70% and below 95%) more than 60% and below 95% apart from the mist degree of light incident side porous semiconductor layer 11e farthest in the near infrared region.
8. promptly, result from above-mentioned 3 and 5,6,7, can think: in the porous semiconductor layer 11 that constitutes by multilayer, the nearest mist degree of porous semiconductor layer in the near infrared region of preferred distance light incident side is more than 1% and less than 11%, is (more preferably more than 70% and below 95%) more than 60% and below 95% apart from the mist degree of light incident side porous semiconductor layer farthest in the near infrared region.
As a comparative example 5～7, use and only stipulated that the suspension of particle diameter has formed porous semiconductor layer, the result is as follows.
(comparative example 5～7: adopt prior art to form porous semiconductor layer)
The method of record had made the titanium oxide of titanium oxide concentration 10wt% during employing Journal of American Ceramic Society the 80th rolled up 3157 pages, and different is: the temperature of autoclave is set to 240 ℃.The average grain diameter of the Titanium particles that obtains (particle A) is about 16nm.Disperse in thing at this Titanium particles, add titanium oxide is the polyethylene glycol (with the pure medicine manufacturing of light, molecular weight 20000) of 20 weight % and is the ethanol of 10 weight % for total liquid.To wherein adding nitric acid, making pH is 1.3, has obtained coating fluid A.The solid constituent of this coating fluid is 10.7%, and titanium oxide content is 8.9%.
For 11.2g coating fluid A, (particle B: particle diameter 100nm～300nm) mix with it disperseed 3 hours with the coating oscillator, obtained coating fluid B to make 0.2g Northeast chemistry system anatase-type titanium oxide.
(particle B: particle diameter 100nm～300nm) 6.7g, polyethylene glycol (with the pure medicine manufacturing of light, molecular weight 20000) 2g, ethanol 2.6g, distilled water 53ml disperseed 3 hours with the coating oscillator, obtained coating fluid C to mix Northeast chemistry system anatase-type titanium oxide.
Porous semiconductor layer 11a uses coating fluid A, and porous semiconductor layer 11b uses coating fluid B, and porous semiconductor layer 11c uses coating fluid C, all adopts sintering condition [1] (5ml/min Oxygen Flow, 450 ℃ of heating down) to carry out sintering. Porous semiconductor layer 11a, 11b, 11c bed thickness are respectively 5 μ m, the thick 15 μ m of 3 laminated meters.
Made 3 dye-sensitized solar cells, its photoelectric conversion efficiency is respectively 6.3% (comparative example 5), 6.5% (comparative example 6), 6.2% (comparative example 7), does not obtain high conversion efficiency.
In addition, form the sample of thick 10 μ m by the mode identical with embodiment 1 by these 3 solar cells, measured photoelectric conversion layer 11a, 11b, 11c be at the mist degree at 800nm place, and its bed thickness conversion mist degree is respectively 2%, 10%, 50% (above be comparative example 5); 13%, 55%, 45% (above is comparative example 6); 11%, 33%, 42% (above is comparative example 7).Hence one can see that: only the particle diameter of the semiconductor particle that comprises in the material solution (or suspension) to porous semiconductor layer 11 is stipulated, can not determine the optical property (being mist degree) of porous semiconductor layer 11 and the character (referring to table 7) of photo-electric conversion element fully herein.
All aspects that it should be understood that execution mode disclosed herein and embodiment all are exemplary and nonrestrictive.Scope of the present invention is not by above-mentioned explanation but disclosed by claims, and can carry out all variations in implication that is equal to claims and scope.
Table 7
The mist degree of porous semiconductor layer 11 The mist degree of the porous semiconductor layer 11a that makes by coating fluid A The mist degree of the porous semiconductor layer 11b that makes by coating fluid B The mist degree of the porous semiconductor layer 11c that constitutes by coating fluid C Conversion efficiency (%)
Comparative example 5 50 2 10 50 6.3
Comparative example 6 52 13 55 45 6.5
Comparative example 7 41 11 33 42 6.2
Industrial application
Photo-electric conversion element of the present invention preferably is applicable to such as various sensors, dye sensitization type solar cell etc.

Claims (10)

1. photo-electric conversion element, it comprises:
Photoelectric conversion layer, carrier transport layer and the pair of electrodes made by the porous semiconductor layer that has adsorbed dyestuff, wherein,
The mist degree of the described porous semiconductor layer of described photoelectric conversion layer in the near infrared region is 60%～95%.
2. the photo-electric conversion element of claim 1, wherein, described porous semiconductor layer is by constituting at the different a plurality of layers of near infrared region mist degree.
3. the photo-electric conversion element of claim 2, wherein, the described porous semiconductor layers that are made of described a plurality of layers increase successively at the mist degree of the near infrared region light incident side from light.
4. the photo-electric conversion element of claim 3 wherein, in the described porous semiconductor layers that are made of described a plurality of layers, is 60%～95% apart from the mist degree of light incident side described porous semiconductor layer farthest in the near infrared region of light.
5. the photo-electric conversion element of claim 4, wherein, described porous semiconductor layer is 3 layers, and, described porous semiconductor layer the mist degree near infrared region nearest apart from the light incident side of light is more than 1% and less than 11%, is 60%～95% apart from the mist degree of light incident side described porous semiconductor layer farthest in the near infrared region of light.
6. the photo-electric conversion element of claim 4, wherein, described porous semiconductor layer is 4 layers, and, described porous semiconductor layer the mist degree near infrared region nearest apart from the light incident side of light is more than 1% and less than 11%, is 60%～95% apart from the mist degree of light incident side described porous semiconductor layer farthest in the near infrared region of light.
7. each photo-electric conversion element of claim 1～6, wherein, described porous semiconductor layer is made of the oxide semiconductor that with the titanium oxide is principal component.
8. each photo-electric conversion element of claim 1～6, wherein, described mist degree is the value of measuring in the random wave strong point of 780nm～900nm.
9. the photo-electric conversion element of claim 7, wherein, described mist degree is the value of measuring in the random wave strong point of 780nm～900nm.
10. solar cell, it has used in the claim 1～6 each photo-electric conversion element.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101872685A (en) * 2010-05-17 2010-10-27 河北工业大学 Solid dye-sensitized nanocrystal/microcrystal silicon composite film solar cell and preparation method thereof
CN102103930A (en) * 2010-11-02 2011-06-22 河北工业大学 Composite thin film solar cell taking microcrystalline silicon layer as incident layer and preparation method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101872685A (en) * 2010-05-17 2010-10-27 河北工业大学 Solid dye-sensitized nanocrystal/microcrystal silicon composite film solar cell and preparation method thereof
CN101872685B (en) * 2010-05-17 2012-06-27 河北工业大学 Solid dye-sensitized nanocrystal/microcrystal silicon composite film solar cell and preparation method thereof
CN102103930A (en) * 2010-11-02 2011-06-22 河北工业大学 Composite thin film solar cell taking microcrystalline silicon layer as incident layer and preparation method thereof
CN102103930B (en) * 2010-11-02 2012-07-11 河北工业大学 Composite thin film solar cell taking microcrystalline silicon layer as incident layer and preparation method thereof

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