TWI245819B - Semiconductor-nanocrystal/conjugated polymer thin films - Google Patents

Abstract

The invention described herein provides for thin films and methods of making comprising inorganic semiconductor-nanocrystals dispersed in semiconducting-polymers in high loading amounts. The invention also describes photovoltaic devices incorporating the thin films.

Description

1245819 发明 Description of the invention (The description of the invention shall state: the technical field to which the invention belongs, the prior art, the content, the embodiments, and a brief description of the drawings) Cross-references for related applications This application is based on US Provisional Patent Application No. 60 Case No. / 365,401 (filed on March 19, 2002); Case No. 60 / 381,660 (filed on May 17, 2002); and Case No. 60/3 81,667 (filed on May 17, 2002) Main non-provisional applications. These U.S. provisional patent applications are hereby incorporated in their entirety for all purposes. Interrelated U.S. patent applications are U.S. Serial No. 10 / 301,510 (filed on November 20, 2002, which claims priority from U.S. Serial No. 60 / 335,435 (filed on 30 November 2001)), and U.S. Serial Numbers ι〇 / 280,135 (which claims priority to US Serial No. 60 / 395,064 (filed on July 12, 2002) and 60 / 346,253 (filed on October 24, 2001). The contents of the two new applications and all provisional applications are hereby incorporated in their entirety for all purposes. Statement of Rights Concerning Inventions Made Under Federally Sponsored Research or Development 15 The portion of the invention described and requested herein is funded by the U.S. Department of Energy using the number AC03- Contract 76SF000-98. The government has certain rights in this invention. [Minghu caterpillar 々 々] 20 The present invention relates to a film and a manufacturing method. The invention also relates to a photovoltaic device incorporating this film.

L Previous Technology I The first too 1% energy battery was manufactured in the 1950s from crystallized stone wafers. At that time, the most efficient installations converted 6% of solar energy into electricity. In the past 50 years, 1245819 发明, invention description The advancement of solar cell technology has formed the most effective Si cells (25%) and commercial Si modules (battery arrays, 10%). Although crystalline and polycrystalline S! Are the most common types of materials used in solar cells, other semiconductors (such as gallium elongation, indium phosphide, and cadmium telluride) are being studied as the next 5 generations for higher efficiency Of solar cells. In particular, a high-efficiency structure (such as a tandem battery in which several band gaps are used, and 8 and Ge are laid in a single device) has achieved a recording efficiency of 34%. Even with these impressive efficiencies, the high cost of making solar cells using conventional techniques limits their widespread use as a source of electricity. Commercially Known Techniques 10 The structure of a silicon solar cell includes four main processing methods: growth of semiconductor materials, divided into wafers, forming such devices and joints, and packaging. For individual cell manufacturing, manufacturing solar cells requires thirteen steps, and of these thirteen steps, five steps require high temperature (3000c_100 (rc), high vacuum, or both. In addition, self-melting The semiconductor growth system of materials is higher than 140 (the temperature of rc is 15 and is in an inert argon atmosphere. In order to obtain a high-efficiency device (> 10%), it is necessary to include a concentrator system that concentrates sunlight on the device, several semiconductors, and In order to absorb more light from quantum wells, or higher performance semiconductors (such as, and InP), the increase in performance results in increased manufacturing costs, which is due to the increased number of manufacturing steps. To date, these high-performance structures are mainly For applications other than ground 20 spheres, such as space shuttles and satellites, in which the efficiency per unit weight is as important as the manufacturing cost. Another problem with conventional solar devices is high-cost manufacturing materials. 1kW modules The output of the stone material required for power is about 20 kg. At $ 20 / gk, the material cost of the electronic material stone material is partially subsidized by the wafer manufacturing department. Within it, 1245819 玖, invention explanatory materials (such as GaAs' is a combination of two toxic gases) which costs $ 40O / kg, which is 20 times higher. Because solar cells are large-area devices, the cost of these materials hinders the production of inexpensive batteries. Therefore, thin-film devices (It has several micron-thick active layers of amorphous Si, CdTe, and CuInSe2) was developed. In 1991, O'Regan et al. Reported the invention of a novel photochemical solar cell containing inexpensive Ti02 nanocrystalline and organic dyes O'Regan et al., Waiwre 353, 737 (1991) 〇 The double-layer device (which is a spin casting from a polythiophene derivative on which the C6G layer is evaporated) has reached a maximum external quantum efficiency of 23% (EQE ). For a single 10-layer device, a higher efficiency of 50% is obtained by blending C6G and MEH-PPV derivatives in a homogeneous film. Further improvements in efficiency are limited by the poor electron transport properties of C60, It is characterized by beating and low overlap between device absorption and solar emission spectrum, Greenham, NC, et al. Corpse Aγ such as v. 5, vol. 54, No. 24, December 1996. 15 It has been suggested in advance in Ju (3 -Hexylthiophene) With CdSe particles, see

Alivisatos et al., Ddv. Maer 1999, 11, number 11. This document only teaches the use of nanocrystals with a size of less than 13 nm, and the devices manufactured cannot approach the efficiency of the present invention. Furthermore, this conventional technique recognizes the solution chemistry problem of nanorods, and does not provide a solution to the problem that can be solved by the present invention as described herein. Inorganic nanorod-based solar cells according to the present invention (which have good transport properties and absorption spectrum, and can also be extended in the near infrared) can achieve an efficiency comparable to that of bulk inorganic semiconductor-based solar cells. The thin film incorporated in the semiconductor / nano crystal according to the embodiment of the present invention provides a solution to the above problems. 1245819 发明 Description of the invention [Summary of the invention] The present invention described herein provides a thin film and a manufacturing method comprising dispersing an inorganic semiconductor-nanocrystal in a semiconductive polymer with a high load. This invention also describes a photovoltaic device incorporating this film. 5 Brief description of the diagram Figure 1 shows the energy level diagram of CdSe and P3HT, which is a schematic diagram showing the charge transfer method between 5 nm CdSe and P3HT. Figure 2 is a schematic diagram of the structure of a nanorod-polymer blend photovoltaic device according to an embodiment of the present invention. 10 Figure 3 shows low-resolution TEM images of a) 7 nm X 7 nm, b) 8 nm X 13 nm, c) 3 nm x 60 nm, and d) 7 nm x 60 nm CdSe nanocrystals.

Figure 4 shows the AFM-TM 15 morphology image of a thin film (rotated from chloroform) composed of 90% by weight of 7 nm x 7 nm CdSe nanocrystals dispersed in P3HT. The scanning area is 5 # m. Figure 5 shows the AFM-TM a film consisting of 90% by weight of 9 nm X 13 nm CdSe nanocrystals dispersed in P3HT (1% by volume and 8% by volume of pyridine in chloroform by spin casting). ) Topographic image and b) phase image. The image is presented in a 5 // m scanning area with the same specifications. 20 Figure 6 shows the surface roughness (hollow circle) of a film composed of 90% by weight of 9 nm X 13 nm CdSe nanorods (cast from various ratios of chloroform in chloroform) dispersed in P3HT. . Maximum EQE (Solid Diamond Shape) is shown with devices made from these films. The line acts as a guide for the eyes. Figure 7a shows 90% by weight of 3 nm X 60 nm CdSe nano 10 1245819 玖, the device of the invention description of the rice rod in P3HT (open circle) and after annealing at 120 ° C (solid distance) Normalize the photocurrent spectrum. Figure 7b shows the EQE ratio of the 90 nm by weight 3 nm X 60 nm CdSe nanorod device and the nanorod-only device in P3HT before and after heat treatment as a function of wavelength. The insertion plot shows the individual 1-transmission spectra of CdSe and P3HT at 3 nm X 60 nm. Figure 8 shows the P3HT pair absorption (solid diamond shape, dotted line), photocurrent (open circle, solid line), P3HT pair absorption of various 3 nm x 60 nm nano rod devices of various series of nano rod concentrations in P3HT, and Relative benefit of light current (solid distance, dotted line) after heat treatment at 120 ° C. Figure 9 shows 90% by weight of 7 nm X 14 nm CdSe EQE in P3HT under -0.1 mW / cm2 irradiation at 515 nm. Insertion plots show the PL efficiencies of 60 wt% 7 nm X 14 nm CdSe in a P3HT sample under 514 nm excitation after heat treatment at various temperatures. 15 Figure 10 shows the EQE spectra of 90% by weight 7 nm X 60 nm CdSe nanorods after P3HT (open circles) and heat treatment at 120 ° C (solid distance shape). Insertion diagram: The corresponding current-voltage characteristics of the device under O.lmW / cm2 irradiation at 515 nm, which includes an open circuit voltage of 0.4V and a fill factor of 0.5. 20 Figure 11a shows the EQO spectra of 90% by weight 7 nm X 60 nm CdSe nanorods with a thickness of 212 nm, 271 nm, and 346 nm from P3HT before heat treatment at 120 ° C. Figure lib shows the thickness of 212 nm, 271 nm and 346 nm from 90% by weight of 7 nm X 60 nm CdSe nanorods in P3HT. 11 1245819 玖, description of the EQO after heat treatment at 120 ° C spectrum. Figure 12a shows the relative promotion of EQE before and after heating the device of Figures 11a and lib at 120 ° C. Figure 12b shows the absolute difference in EQE before and after heat treatment. 5 Figure 13a shows the TEM of a 20% by weight 3 nm X 60 nm CdSe nanorod and P3HT film cast from chloroform. Fig. 13b shows the TEM of the same nanocrystals of Fig. 13a from 10 vol% pyridine in chloroform solution when cast. FIG. 14 shows a TEM of a cross section of a 100 nm thin film composed of 60% by weight of 10 nm X 10 10 nm CdSe nanocrystals in P3HT. Figure 15a shows a 7 nm X 60 nm CdSe nanorod. Figure 15b shows the TEM of a cross section of a 100 nm thin film composed of a 40% by weight CdSe nanorod in P3HT. Figure 16 shows that the length of a 7 nm diameter nanorod is continuously increased from 7 nm to 30 nm and 60 nm under 15 0.084 mW / cm2 at 515 nm. For 90% by weight of P3HT The EQE of the device increased to almost 54% by a factor of 3. Figures 17a-c show TEMs of 7 nm diameter nanocrystals with a) 7 nm, b) 30 nm and c) 60 nm in length. The scale setting is 50 nm, 20, and all TEMs are the same scale. Fig. 18 shows the EQE of a device of 90% by weight of a 3 nm X 100 nm branched CdSe nanorod in P3HT as a function of pyridine concentration. Figure 19a shows the unaligned tetrapod nanocrystals. 12 1245819 发明, description of invention Fig. 19b shows the tetrapod nanocrystals arranged. Figure 20 shows the EQE spectra of a series of devices with different film thicknesses of 90% by weight of 7nm X 60 nm CdSe in P3HT. Figure 21a shows the EQE spectra of 7 nm X 7 nm CdSe at 90% by weight and 5% by weight in P3HT for various film thicknesses. Figure 21b shows the corresponding absorption spectra of these devices as a function of increasing thickness. Figure 22a shows a TEM of 40% by weight of 5 nm CdSe nanocrystals treated with TOPO-treated nanocrystals in P3HT. 10 Figure 22b shows a TEM of 40 wt% 5 nm CdSe nanocrystals of T1 treated nanocrystals crystallized in P3HT. Figure 22c shows a TEM of 40 wt% 5 nm CdSe nanocrystals treated with pyridine-treated nanocrystals in P3HT. Figure 23a shows the I-V characteristics of 15% 90% by weight 7 nm X 60 nm CdSe nanorods in P3HT at 515 nm under 0.1 mW / cm2 irradiation. Figure 23b shows the solar cell characteristics of the same device shown in Figure 23a. It is measured with an analog AM 1.5 Global light source, including a short circuit current of 5.7 mA / cm2, an FF of 0.42, and an open circuit voltage of 0.67V, yielding 1.7% Solar power conversion efficiency.

20 Figure 24 shows the I-V curve of the physical phase and the typical I-V curve found experimentally. [Embodiment 3 The detailed description of a preferred embodiment is described in an embodiment of the present invention, and a thin film is disclosed which has a semiconductivity of 13 to 1245819 玖, a 5% less semiconductor-nanocrystal buried in the description of the invention. In another embodiment, a conjugated polymer discloses a photovoltaic device including the film of the present invention. 5 In another embodiment of the present invention, a method for manufacturing a polymer film is disclosed, which includes washing a semiconductor-nanocrystal coated with a surfactant at least once with a solvent, and washing the cleaned semiconductor-nanocrystal and semi-crystal. The conductive polymer is co-dissolved in the binary solvent mixture and the mixture is allowed to settle. In another embodiment of the present invention, a method for manufacturing a photoactive film is disclosed, comprising dispersing semiconductor nanocrystals having an aspect ratio greater than 2 in a semiconducting conjugated polymer to provide polymer-nanocrystals. The composite, and the film on which the composite is deposited, so that the nanocrystalline is buried in the polymer at greater than 5% by weight. In another embodiment of the present invention, a photovoltaic device is disclosed, where U includes a conjugated conductive polymer layer having a semiconductor-nanocrystal buried therein, and the device is fully irradiated at AM 1.5 Has a power conversion efficiency of more than 1%. -In another embodiment of the present invention, a photovoltaic device is disclosed, which includes a first planar electrode including a thin film of a semiconducting co-consumable polymer with a semiconductor-nanocrystal buried therein. The thin film is deposited on the first planar electrode and the second electrode, which is opposite to the first electrode and the electron hole injection layer, which is disposed between the thin film polymer layer and the first planar electrode. , Semiconductor-nano junction is more preferably about 5 and 50

In the preferred embodiment of the present invention, the aspect ratio is preferably greater than 5, and the crystal has a value greater than 2. The best system is 14 1245819. The invention description is about 10. In a preferred embodiment of the present invention, the dispersion or embedding of semiconductor-nanocrystals in a semiconductive polymer is disclosed. Preferably, this "loading amount" is an amount greater than 5% by weight. More preferably, this content is between 20 and about 95% by weight. 5 More preferably, the content is between 50 and about 95% by weight. Optimally, this content is about 90% by weight. In a preferred embodiment of the present invention, the semiconducting polymer will be selected from the group consisting of trans-polyacetylene, polypyrrole, polythiophene, polyaniline, poly (p-phenylene) and poly (p-phenylene) -Polymers or blends of vinylidene), polyfluorene, polyaromatic amines, poly (ethynyl- vinylidene) and their soluble derivatives. Preferred are (poly (2-methoxy5- (2'-ethylhexyloxy) -p-phenylene vinylene) (MEH-PPV) and poly (3-hexylthiophene) (P3HT), and P3HT is Best. In the preferred embodiment, the semiconductor-nano crystals include rods having a length greater than about 20 nm. More preferably, rods having a length between 20 and 200 nm. More preferably 15 systems having a length between about 60 and 110 nm In a more preferred embodiment, the present invention discloses the use of III-V, III-V, IV semiconductors and tertiary mica copper ore. More preferably CdSe, CdTe, InP, GaAs, CuInS2, CuInSe2, AlGaAs, InGaAs, Ge, and Si are more preferably CdSe. 20 Preferably, the semiconductor nanocrystals are branched nanocrystals. More preferred nanocrystals have four arms and are tetrahedral symmetrical. Preferably, the film of the present invention It has a thickness of about 200 nm. Preferably, the method for manufacturing the thin film of the present invention uses a binary solvent mixture, wherein at least one solvent is selected from the group consisting of pyridine, chloroform, toluene, dioxobenzene, 15 1245819 玖, invention description, Water, digas benzene, dichlorotoluene, and alkynylamine (wherein the alkynyl chain may be branched or unbranched, The length is between 2 and 20 carbon atoms), butanol, methanol and isopropanol. The best is pyridine in chloroform. Preferably, the content of this binary solvent mixture is between M5 vol%, 5 more The preferred range is 4-12 vol%, and the most preferred is 8 vol%. Another embodiment of the present invention described herein discloses a method for manufacturing a polymer film having semiconductor nanocrystals incorporated therein, wherein The first step is to clean the semiconductor nanocrystals coated with the surfactant at least once with a solvent (preferably, Ubitu). 10 Another embodiment of the present invention described herein is a method for manufacturing a polymer film Including a thermal annealing of the deposited film at a temperature of 60 ° C to about 200 ° C. It is preferably about 120 ° C. In another embodiment of the present invention, a photovoltaic device 'its in The top of the ITO electrode incorporates a pedOT: PSS (poly (ethylene-dioxy 15-yl) thiophene: poly (styrene sulfonic acid)) electron hole transport layer. The semi-V-body-nanocrystal means that it contains Semiconducting crystalline particles of all shapes and sizes. Preferably, they have at least one The size is about 10011111, but it is not limited. The rods can have any length. "Nanocrystals, nanometer rods, nanoparticle, and nanoparticle, can be used interchangeably here. Some of the invention Example 20 'Nano-crystalline particles may have two or more sizes that are less than about fine. T-crystalline crystals may be core / shell or core-type. For example, certain branches according to certain examples of the present invention The shaped nanocrystalline particles may have arms having an aspect ratio greater than about 1. In other embodiments, these arms may have an aspect ratio greater than about 5 ′ and, in some cases, greater than about 10, etc. In some embodiments, the width of these arms can be less than about 200, 100, or even 50 nm. For example, in an exemplary tetrapod with a core and four arms, the core may have a diameter of about 3 to about 4 nm, and each arm may have about 4 to about 50, 100, 200, 500, or even greater than about 1000 nm Its length. Of course, the tetrapods and other nanojunction 5 crystal particles described herein may have other suitable sizes. In the embodiment of the present invention, the nanocrystalline particles may be monocrystalline or polycrystalline in nature. The present invention also considers using nanorods of CdSe and CdTe with aspect ratios higher than 20 (even up to 50) and lengths greater than 100 nm, which are formed according to the methods described in the literature, see 404 by Peng, XG · et al. , 59 (2000) and Peng, Z · A · et al. 10 J. d / n · CTzem. 123, 183 (2001) 〇 The length of the semiconductor-nanocrystalline rod used here has a length between 20 and 200 nm . In a preferred embodiment, the semiconductor-nanocrystal comprises a rod having a length greater than about 20 nm. More preferred are rods with lengths between 20 and 200 nm. More preferably, it is a rod with a length between about 60 and 110 nm. 15 "At least a part of the semiconductor-nanocrystal has an aspect ratio greater than about 2" means that if the semiconductor-nanocrystal is an unbranched rod, at least a part of the total amount of the rod will have a greater than about 2 aspect ratio. This content can be as high as 100%. Furthermore, this means that if the nanocrystalline branched semiconductor-nanocrystal (including tetrapods of course), at least a part of the shell Γ means that at least one branch has an aspect ratio of 20 greater than 2. Aspect ratio The length defined as the longest dimension of the rod divided by its diameter. In the case of branched nanocrystals, the aspect ratio of branched nanocrystals is defined as the length of the longest branch divided by the diameter of the longest branch. "Semiconductor-nanocrystalline branched nanocrystals" means at least 1% by weight of nanocrystalline branched nanocrystals. It should be understood here that 17 "1245819", "a part" defined in the description of the invention also includes 100 %, That is, "the whole part". Although CdSe and CdTe semiconductor-nanocrystalline systems are preferred, the nanocrystalline particles may include other suitable semiconductor materials and are rods, shaped particles, or spheres. For example, the particles may include semiconductors such as compound semiconductors. Suitable compound semiconductors include group II-VI semiconducting compounds such as MgS, MgSe, MgTe, CaS, CaSe, CaTe, SrS, SrSe, SrTe, BaS, BaSe, BaTe, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgSe and HgTe. Other suitable compound semiconductors include semiconductors of the III-V group, such as GaAs, GaP, GaAs-P 10, GaSb, InAs, InP, InSb, AlAs, A1P, AlGaAs, InGaAs, and AlSb. The use of Group IV semiconductors such as germanium or silicon is also feasible under certain conditions. In other embodiments, the particles may include a dielectric material, such as SiC, SiN, or any other material capable of exhibiting polymorphism. It also contains tertiary mica copper ore, such as CuInS2 and CuInSe2. Certain metals (such as Fe, Ni, 15 Cu, Ag, Au, Pd, Pt, Co, etc.) can also exhibit polymorphism and can be used in embodiments. Rod-shaped, arrow-shaped, teardrop-shaped, and tetrapod-shaped semiconductor nanocrystals are defined in Manem et al., CAem. Xin c. 2000, 12, 12700-12706, the contents of which are incorporated herein for all Purpose. Nanocrystalline particles according to embodiments of the present invention may have unique optical, electrical, magnetic, catalytic, and mechanical properties, and may be used in several suitable end applications. It can be used, for example, as a filler for composite materials, a catalyst, a functional element of an optical device, a functional element of a photovoltaic device (for example, a solar cell), a functional element of an electric device, and the like. "P3HT" refers to poly (3-hexylthiophene), which contains regioregularity 18 1245819 发明, description of the invention P3HT, which includes the regioregularity P3HT of head joint and head to tail. P3HT is preferred. The present invention contemplates that any semiconducting conjugated polymer that can be treated from solution can act in accordance with the present invention. "Semiconducting polymer" means all polymers having a 7Γ-electron system. Non-limiting examples include trans-polyacetylene, polypyrrole, polythiophene, polyaniline, poly (p-phenylene) and poly (p-phenylene-phenylene), polyfluorene, polyaromatic amines , Poly (ethynyl-ethenyl) and the above-mentioned soluble derivatives. Examples are (poly (2-methoxy, 5- (2'-ethylhexyloxy) -p-phenylene vinylene) (MEH-PPV) and poly (3-hexylthiophene). Particularly preferred is poly 10 ( 3-hexylthiophene), P3HT. The present invention also considers the use of conjugated polymers that can be solution-processed or melt-processed because the bulk side groups are attached to the main car chain or the car polymer is included in a One or more components are within the copolymer structure of non-co-owners. Non-limiting examples include poly (, 4'-diphenylene diphenyl vinylene), poly (1,4-phenylene- 1-phenyl vinylene and poly15 (1,4-phenylene diphenyl vinylene, poly (3-alkyl-gall) and poly (2,5-dialkoxy-p-phenylene vinylene) It is necessary to understand that a semiconductive conjugated polymer refers to a mixture of polymer blends of a series of semiconductive conjugated polymers. Therefore, the nanocrystalline system is buried or dispersed in the blend or mixture. The present invention further considers semiconductor-nano crystals, rods, which can be arranged by any of the techniques known in the art of arranging crystals. "Photovoltaic device" means Contains the type of device structure known in the art. Exemplary photovoltaic devices are described in, for example, Science, volume 295, pages 2425-2427, March 29, 2002, the contents of which are incorporated herein by reference The exemplified photovoltaic device may have nano 19 1245819 玖 in the adhesive, crystal particles of the description of the invention. Then, the composition is sandwiched between two electrodes (for example, an aluminum electrode and indium tin oxide) on a substrate. (Electrode), a photovoltaic device is formed. "Two Fan Solvent System" refers to a system containing two solvents, and _ can be a ligand, which is also a solvent. For example, pyridine in aerosol., Binary solvent 5 agent system, also refers to a system containing at least -solvent and non-solvent ligands, for example, xylene and phosphonic acid. Dibenzobenzene semiconductor nanocrystalline solvent, and phosphonic acid system But not solvent. Appropriate methods for making the films described herein are known. Non-limiting examples of various self-solution coating and printing techniques include spin coating, doctor blade coating 10, dip coating, inkjet Printing and _screen printing. All technologies in Generally referred to as "deposition". That is, the thin film of the present invention needs to be deposited, deposited, on certain types of substrates. The complementary electronic properties of inorganic and organic semiconductors can be used to form electroactive bonds. Charge transfer is high The affinity between inorganic semiconductors with electronic affinity and organic molecules and polymers with relatively low ionization potentials is relatively advantageous. In one embodiment of the present invention, semiconductor nanoparticle (such as Cdse nanocrystal) and conjugated polymer (Such as P3HT) combined to generate a charge transfer connection with a high interface region, which results in a photovoltaic device with improved efficiency. From the CdSe nanocrystal and the energy level diagram of P3HT, it can be seen that the CdSe system accepts electrons and ρ3Ητ 20 Accepts electron pores (No. 丨 _). The ligands on the surface of the nanocrystalline crystals regulate the interaction with the polymer. After casting, the ligand on the cdSe surface can be replaced or removed by chemically cleaning the nanocrystals or heat-treating the CdSe-P3HT blend film. The effect of charge transfer and transport is determined by the form of the blend. 20 1245819 发明, description of the invention. The aggregation of nanocrystals in solution and polymer depends on the van der Waals interaction strength between the particles, and therefore on the separation and size of the nanocrystals. A balance between the aggregation effect for transporting electrons and the dispersion effect for more efficient charge transfer is necessary. The inventors have surprisingly discovered that precise control of morphology is obtained by using a solvent mixture. A solvent mixture according to an embodiment of the present invention containing pyridine, which is a ligand and helps dissolve nanocrystals, can affect the dispersion of nanocrystals in a solution. Because spin casting is a non-equilibrium method, the dispersion of nanocrystals in solution can be maintained in the polymer. 10 According to an embodiment of the present invention, the solvent mixture is used to control phase separation up to the nanometer size. The inventors have surprisingly discovered that solvent mixtures can be used to control phase separation in thin films with high nanocrystalline concentration (up to 90-95% by weight) in polymers (especially P3HT) to 亳 micron size. The purpose is to promote the solubility of nanocrystals by using a solvent 15 that is good for nanocrystals (especially CdSe) and ligands and a solvent that is good for solution-treated polymers. A preferred example is a strongly bonded Lewis base, pyridine, which has a relatively low boiling point of 116 ° C, and is easily selected as a ligand for nanocrystals due to its ease of removal. Pyridine-treated nanocrystals of various shapes and sizes are co-dissolved with P3HT in a mixture of 4% to 12% by volume of 20% pyridine in chloroform, which is produced by dispersed particles in the polymer during spin casting. Uniform thin film. The preferred ton sigma content to cover the nanocrystalline surface is determined by the number of non-passivated Cd surface locations on the nanoparticle. Pyridine is compatible with chloroform. In this way, it has a twofold increase in solubility for nanocrystals: (a) Nanocrystals coated with gadolinium are better than their bare counterparts. 21 1245819 发明, description of the invention It is soluble in chloroform, and (b) it is highly soluble in an excess of pyridine that is not bound to nanocrystals. However, too much pyridine needs to be avoided because it regulates the precipitation of P3HT (which is extremely soluble in chloroform but different from pyridine). Therefore, there are three types of solubility range. 5 I. Low Pyridine Concentration Range: Insufficient solubility of nanocrystals results in large-scale phase separation of blend films promoted by aggregation of nanocrystals. II. Intermediate pyridine concentration range: If the polymer is still sufficiently soluble in the mutual-solvent blend of the two solvents, the promotion of the solubility of the nanocrystalline components of the blend solvent will result in dense mixing of the two semiconductors, and thus the spin coating Avoid 10 to avoid phase separation. III. High pyridine concentration range: Due to the solvent of the pyridine non-polymer component, we expect to promote large-scale phase separation by polymer chain aggregation. To study the morphology of nanocrystalline crystalline-polymer films, photosensitive techniques (such as atomic force microscopy (AFM)) and bulk photosensitive techniques (such as transmission electron microscopy (TEM)) are used. An example of category I is shown in Figure 4 for 90% by weight 7 nm X 7 nm nanocrystals in P3HT, which is rotated from a single chloroform solvent. Figure 4 shows phase separation on the scale of several micrometers. Because the film scatters light, it can also be detected under an optical microscope, even with the naked eye. Light scattering in thin-film photovoltaic devices is undesirable because it reduces the fraction of absorbed light. The study of the surface of nanocrystalline crystalline-polymer blend films can be greatly promoted by using AFM in shooting mode (TM), because it is generally possible to identify local differences in film composition by comparing phase and morphological images . As an example, the transition from category I to category II is shown in Figure 5. Figure 5 shows the 9 nm X 13 nm nanorod blend film obtained by rotating a solvent mixture with a low and intermediate pyridine concentration of 22 1245819 玖 and a description of the invention. AFM-TM morphology and phase image of 5 // m scanning area. Although the morphology of these films is sufficient for low-degree-pyridine concentrations, intermediate concentrations produce smoother films. The phase images of the corresponding AFM-TM proved that the surface roughness was related to phase separation. Nanocrystals and phase separation between polymers do not result in a single material region, so it is not possible to identify individual polymers and nanocrystal regions. At low pyridine concentrations, there is clear evidence of local changes in film composition, while at intermediate pyridine concentrations, the phase image is very smooth. Therefore, we can individually classify these two concentrations into category I and category II. 10 In another embodiment of the present invention, the high-load semiconductor-nanocrystals in the conjugated polymer according to the present invention are considered to cause a "smooth" film surface. This can be quantified. To quantify these results, the root mean square (RMS) of the film roughness was determined from the AFM morphological image as a function of the concentration of pyridine (Figure 6). As the pyridine concentration increases from 0 to 5 vol%, the RMS coarse 15 roughness decreases by an order of magnitude. The concentration of pyridine between 5 and 12% by volume has only a slight increase in RMS roughness, and when the concentration of pyridine takes 12 to 20% by volume, it has an order of magnitude increase. Using the above scheme, we can classify the concentration range of 0 to 5 vol% as category I, 5 to 12 vol% as category II, and 12 to 20 vol% as category III. These concentration values are 20 pairs of nanocrystals and polymers with a fixed overall concentration in the binary solution. For 90% by weight of CdSe nanocrystals used in P3HT here, the partial concentrations were 45 g / liter and 5 g / liter, respectively. It is important to understand that the concentration indicated for cleaning effects can vary by up to 20% and still be effective. Charge separation occurs only for the excitation-diffusion region at the nanocrystal-polymer interface. The single material region size is reduced due to better nanocrystalline dispersion, and an increase in external quantum efficiency (EQE) is expected. EQE can be used as a measure of charge separation efficiency if the following quantities can be compared to a group of devices: ⑴ incident light intensity, (ii) fraction of absorbed light, and (iii) charge collection efficiency at the electrode 5 (which is mainly determined by Electrode selection). These three conditions are met for the device presented in Figure 6 with EQE data. Figure 6 shows the pyridine dependence of EQE for a blend of P3HT and CdSe nanocrystals of 9 nm X 13 nm. From period I to period II, the EQE line increased by a factor of 1.4, and then decreased again for the region III line. In the preferred embodiment, 10 35% maximum EQE is found for a concentration of 8 vol% pyridine in a solvent mixture (ie, a binary solvent system). A similar dependence of EQE on the concentration of pyridine in a binary solvent system resides in spherical nanocrystals dispersed in P3HT. The maximum EQE is also at 8 volume% of the pyridine concentration, which is comparable to the value found for nanorods with low aspect ratios as described above. For a fixed nanocrystal concentration, the optimal pyridine concentration is determined by the surface to volume ratio of nanocrystals. For devices containing 3 nm X 100 nm nanorods, the best device is cast from a solution containing 12% by volume ° specific bite, while devices with 7 nm X 60 nm nanorods require only 4% by volume σ ratio 唆. A 3 nm diameter nanorod has a surface-to-volume ratio that is 2 20 factors higher than a 7 nm nanorod. More pyridine is needed to maintain the surface of the thinner nanorods covered with pyridine, so the bound pyridine molecules are in dynamic equilibrium with the free σ-pyridine in the solution. In another embodiment of the present invention, the binary solvent mixture used in accordance with the present invention can be changed by replacing pyridine with another ligand. For example, CdSe 24 1245819 rhenium, description of the invention, CdTe and InP nanocrystals are synthesized in a mixture mainly composed of TOPO or TOP and different phosphonic acids. After the nanocrystals are recovered and stored, they have a large excess of TOPO (or TOP) in the product, and the nanocrystals are passivated by this organic surfactant. Nano crystals with TOPO shells are less susceptible to oxidation and are easily soluble in a variety of solvents, including toluene, chloroform, hexane, THF, pyridine and butanol. TOPO can be substituted with other ligands of cadmium, such as thiols, amines and other phosphine oxides and phosphonic acids, as shown below. 0 TOPO τι pyridine

10 The non-conjugated ligand is not absorbed in the visible part of the electromagnetic spectrum, and the light applied to the solar cell generates a current. Polythiophenes with attached phosphine oxide or phosphonic acid functionality can be bonded to the surface of CdSe and other semiconductor-nanocrystals. These conjugated ligands with longer conjugates (higher than 4 monomer units) were absorbed in the visible light region of the electromagnetic spectrum and contributed to photocurrent at 25 1245819 玖. Therefore, their use is based on this Consider an embodiment of the invention. Non-limiting examples of phenylphosphonic acid are preferred ligands. The energy levels of oligothiophenes with more than 10 monomer units are close to the parent polymer (P3HT). TnPA is a thiophene (thiophene ring with η number 5) phosphonic acid as shown below. There are three preferred thiophene derivative ligands considered in the present invention. The number of thiophene rings can be varied, and phosphonic acid, phosphine oxide, or oligofluorene amine can be used.

Because the large agglomerates are tightly bound to the nanocrystals and can interact densely with the polymer 10, it helps to improve the charge transfer rate between the two semiconductors. Oligomers that also have polymer-like side chains help a large number of nanocrystals repel each other and disperse well within the polymer. In the preferred case, nanocrystals are blended with polymers containing chemical functionalities such as phosphines and phosphine oxides bound to the nanocrystals. In this example, the polymer can be close to 15 nanometer crystals to promote fast and efficient charge transfer. In order to replace TOPO or other synthetic solvents, nanocrystals are washed with a suitable solvent that is a special surfactant for nanocrystals. Then, the nanocrystals are dissolved in a solvent, an excess of the desired ligand is used, and refluxed at a high temperature for several hours. The high temperature system ensures the intermittent removal of ligands from the nanocrystalline surface. 26 1245819 玖, description of the invention, and this excess maintains the equilibrium of the new ligand on the nanocrystalline surface. Another effective chemical treatment to reduce the exposure of nanocrystals to high-temperature oxygen and water is to dissolve nanocrystals in excess of the substituted ligand, and then precipitate the particles in the solvent of TOPO or other synthetic solvents, and after centrifugation Discard the upper layer 5. Pyridine (with a boiling point of 116 ° C) is one of the most easily substituted ligands, and is preferably used with CdSe. Nanocrystals passivated with pyridine are more insoluble than those covered with TOPO, but they can be stripped easily by drying or heating the nanocrystals. In a photovoltaic device made from a nanocrystal-polymer blend, the ligands on the 10nm crystal determine the film morphology and the degree of microphase separation. The morphology of the blend of CdSe with various ligands (including TOPO, pyridine, and modified TOPO, one of which has an octyl moiety substituted with a thiophene ring (T1)) is shown in Figure 22. As a non-limiting example, TOP0 blunt CdSe nanocrystals with non-polar alkyl chains can be uniformly dispersed in the non-polar matrix of P3HT. The clear spacing between the particles corresponds to the approximate length of 11 A, the TOPO molecule (Figure 22a). When THP0 was modified by replacing a octyl chain with a thiophene ring to produce T1, these nanocrystals behaved differently from particles coated with TOPO when dispersed in P3HT (Figure 22b). Nanocrystalline system 20 coated with T1 aggregates more easily than particles coated with TOPO, and aggregates of CdSe nanocrystals are combined into nanoparticle lines. Although not limited by any theory or principle, it is possible that the thiophene ring on the T1 molecule and the thiophene ring on the polymer produce a 7Γ-stack, which causes the nanocrystals to be aligned along the polymer chain. The presence of surfactants on the surface of nanocrystals can be distinguished from the particles within the aggregates and between the particles of the nanocrystalline chains 27 1245819 发明, description of the invention. In contrast, nanocrystals coated with pyridine aggregated in P3HT (Figure 22c). Although not limited by any particular theory or principle, it may be because pyridine is a weak Lewis base, and some pyridine is removed from the nanocrystalline surface during the evaporation of the solvent during film casting. Therefore, the van der Waals interaction between the highly polar nanocrystals in the non-polar 5 P3HT creates a micro-scale phase separation between the organic and inorganic components of the composite. Nanocrystalline crystals cleaned with pyridine are in closer contact with nearby particles. In this way, there is no clear separation of nanocrystalline crystals in the film as observed with TOPO-coated particles. Similar differences in the behavior of the poly 10 clusters between nanocrystals coated with TOPO and pyridine were observed in the polymer MEH-PPV, which is more polar than P3HT. It should be understood that the present invention considers, as a preferred embodiment, a non-self-synthetic treatment method which actually replaces 95% of the surfactant on the rod. Intuitively, it may be possible to remove more residual surfactant by washing three times, and it is better because the surfactant interferes with charge transfer. However, the inventors have surprisingly discovered that with just one cleaning step, certain surfactants are retained, resulting in a photovoltaic device that is larger and more predictable than expected. The EQE of this device is improved by 3 to 5 times compared to the device washed three times. Nano crystals with a diameter of 5 nm were washed three times in methanol to remove excess 20 TOPO, and then dissolved in the minimum amount of pyridine (50 // 1 per 100 ml of CdSe series) and precipitated three times in hexane to obtain Pyridine particles on the surface. Nanocrystals washed with methanol are first refluxed with pyridine instead of TOPO, precipitated with hexane, and then refluxed in a T1 solution in toluene for 12 hours to produce T1 coated particles. The film was obtained by spin-casting a 40% by weight nanocrystalline solution in a simulated P3HT as a result of self-dissolving gas on a NaCl IR window. These samples were immersed in water to float the blend film, and a copper TEM grid with porous carbon was used to pick up the film. In another embodiment of the present invention, the inventors have surprisingly discovered that heat treatment 5 is an effective method to promote the mobility of organic molecules bound to an inorganic surface, and that the nanocomposite treatment near the polymer glass transition temperature can make the film interior These molecules move towards the surface. In organic blends, thermal annealing has been used to promote the equilibrium morphology of spin-cast films and, in some cases, to promote phase separation and crystallization within the compound. For nano-polymer blends, 10 heat treatments can improve the nanocrystal-nano crystal and nanocrystal-polymer interfaces to unexpectedly promote charge transfer and transport, and improve the performance of photovoltaic devices. Excessive pyridine in the binary solvent (to control the dispersion of nanocrystals in the polymer) will be shown as a non-radiative recombination center for excitons generated in P3HT. Therefore, these excitons do not contribute to the photocurrent. The thermal annealing of the thin film according to the embodiment of the present invention results in the removal of excess unbound pyridine in the interfacial pyridine and polymer regions. A significant promotion of EQE was observed in the heated device, which may be related to the recovery of these excitons lost for charge transfer and photocurrent generation. The normalized photocurrent measured on a 90% by weight 3 nm X 60 nm CdSe nanorod in P3HT 20 by spin casting of 10% by volume of pyridine solvent in chloroform is shown in Figure 7a (hollow (Round, before annealing; solid distance, after annealing). The absolute maximum EQE is 15% at 455 nm under flowing argon under 0.1 mW / cm2 irradiation. When heated at 120 ° C under a reduced pressure of about 50 millitorr for 3 hours and cooled for 8 hours to room temperature, the photocurrent of the same device was greatly improved by 29 1245819 玖, the description of the invention (Figure 7a), which is higher than generally expected . While not intending to be bound by any particular theory or principle, these unexpected results can be explained as follows. The ratio of the photocurrent of the heated device to the photocurrent of the device before heating shows an overall promotion with a factor of 2.5, and it approaches 650 5 nm with a particularly strong increase by a factor greater than 6, and has a shoulder at 700 nm ( Figure 7b). To understand the origin of this red EQE promoting wave crest, a device with only 3 nm X 60 nm CdSe nanorods was manufactured and heated under the same conditions. The photocurrent analysis before and after the heat treatment showed only a promotion feature centered around 700 nm. Therefore, we attribute this red shift in the photocurrent of the blend 10 to the nanorod. Therefore, without being limited by a specific operating theory or mechanism, it is assumed that heat treatment is believed to facilitate the removal of interfacial pyridine and bring nanorods closer together, resulting in unexpected and surprisingly superior efficiency. The aggregation of adjacent nanorods may improve the electron transport between the nanorods, so the separation distance between the beating steps is reduced. In addition, the removal of the interfacial pyridinium can also promote the charge transfer between CdSe and P3HT by bringing the two materials into closer electronic contact. These two effects are most likely to contribute to the overall photocurrent promotion of all factors of about 2.5 of the absorbed wavelength. The maximum photocurrent increase occurred in the region between 500 nm and 700 nm, where a factor greater than 6 was obtained for a 90% by weight CdSe blend device, and both CdSe and P3HT contributed significantly to light absorption. To determine the relative benefit, we compare the fraction of light absorption with the fraction of photocurrent generated by each material component. The absorption spectrum of a series of devices with varying CdSe concentration can be adapted to the linear combination of individual CdSe and P3HT spectra (Figure 8) 30 1245819 发明, invention description The absorption between 400 nm and 700 nm of the blend device after heating is not significant Variety. For concentrations greater than 40% by weight, the benefit of P3HT concentration for photocurrent is significantly less than the proportion of light absorbed by the polymer. In a device with 90% by weight CdSe, P3HT helps to absorb 61% of the light, but polymer 5 only contributes 8% of the photocurrent. This means that the large amount of light absorbed by P3HT does not contribute to the current generation and is lost to non-radiative or radiative recombination paths. However, when these devices are heat treated at 120 ° C, changes in the photocurrent spectrum produce the benefit of P3HT, which is closer to the ratio of light absorption. For a 90 wt% CdSe device, the P3HT portion of the photocurrent has dramatically increased to 10 66%, which is comparable to 61% of the absorbed light in P3HT. This external quantum efficiency is observed at 60 ° C to 160 ° C, and decreases again at 180 ° C, as aluminum migrates through the film and the device degrades, Figure 9. Correspondingly, the PL efficiency (which is a function of processing temperature) of 60% by weight 0 (186 blend film) rose to 120 ° C, then decreased, and remained fixed at higher temperatures (insertion of Fig. 9 15 Figure). The present invention considers that the thermal annealing temperature can be as high as 200 ° C. These unexpected effects can be explained as follows. Because the PL efficiency of the CdSe in the blend is less than 0.1%, the PL of the sample is mainly generated from P3HT. Heating of P3HT It is known to cause promoted crystallinity, which terminates PL efficiency. This effect is observed in heated P3HT films at temperatures as low as 40 ° C. 20 Therefore, the increased crystallinity is explained by doping above 120 ° C. The slight decrease in PL efficiency observed in the polymer film, but cannot explain the substantial increase in PL efficiency below 120 ° C. At low temperatures, the excess in the polymer is removed ^ The processing efficiency of the PL efficiency increases with the increase in bite P3HT The possible reason for the increase may be because some of the protons absorbed in P3HT are aggregated in the untreated film 31 1245819 发明, invention description non-light shot recombination at the 17 bite position in the composition and does not help PL After heat treatment, these protons can In radiation decay and charge transfer. Therefore, the removal of excess pyridine caused a larger P3HT benefit to the photocurrent, leading to the promotion of EQE observed in the region between 500 nm and 700 nm. 5 According to the preferred embodiment of the present invention Heat treatment is important to promote EQE for high aspect ratio nanorod devices that have a high surface area to volume ratio and require a higher pyridine concentration (> 8% by volume) in a spin casting solution. The device composed of equal nanometer rods has a large area of nanometer rod-nanometer rod and nanometer rod-polymer interface, which contains pyridine and a large amount of excess pyridine. The removal of this pyridine has the highest A large number of EQE improvements up to a factor of 6 are observed in Figure 7. Conversely, a 7 nm X 60 nm size nanorod is blended with P3HT in a solvent with only 4% by volume of pyridine, and heated after The maximum EQE increase is only a factor of 1.3 (Figure 10). The present invention considers the use of a nanorod 15 with a low surface area to volume ratio. Therefore, removing the pyridine from the film (< 200 nm) is only at low pressure (&10; 6 mbar) pumped from the sample And no performance improvement was observed during heat treatment. Furthermore, the heat treatment of the thin film is not good for open circuit and filling factor, because aluminum diffuses through a significant part of the device. Within a range of thicknesses ranging from 100 nm to 350 nm within P3HT 20 The 90% by weight 7 nm X 60 nm nanorod CdSe device is improved when the thickness is higher than 200 nm at 120 ° C (Figure 11). As the thickness of the device increases, the relative promotion of EQE also increases ( (Figure 12a). The absolute improvement of EQE after heat treatment also increases with thickness (Figure 12b), but due to the poor transport properties of the thickest device, the thickness is limited at 346 nm. 32 1245819 玖, description of the invention. Hybrid nanorod-polymer solar cells become more efficient through nanorod arrangement and rod synthesis longer than 100 nm. Thicker films with higher optical density to absorb more sunlight can be used . For these thick films, heat treatment is better for implementing high performance devices. 5 In another embodiment of the present invention, the inventors have surprisingly implemented unpredictable strategies to increase carrier mobility and improve charge collection, resulting in improved battery performance. For blends of electron transport materials and electron hole transport materials, the generation of percolation paths is necessary to transport the charge. In the dispersion of nanocrystals and polymers, the termination of these paths to electrons serves as a trap 10 or recombination center. Increasing the size of nanocrystals will reduce the number of these terminals and thus promote performance. However, in order to achieve the efficiency observed for commercial solar cells, it is desirable to have a higher carrier mobility and a lower recombination rate. A nanorod with a length similar to the thickness of the device can have a guided path, during which the carrier mobility is similar to a 15-degree wire. Therefore, the problems of percolation and beating can be eliminated. By controlling the aspect ratio of the CdSe nanorods in P3HT, the inventors have surprisingly adjusted the length gauge and electronic transport direction via a thin film pv device. As the aspect ratio of the nanocrystals increases from spherical to rod-like, the self-molecular range 7 is closer to the wire in the space of the shifting angle, and becomes less soluble. In Fig. 20 13a, nanorods are aggregated in p3HT to form single islands, which are formed by thin-film self-imitation casting over several micrometers. However, for the same concentration, nanorods are dispersed in the polymer when cast from a mixture of chloroform / chloroform solvent, Figure 13b. Dispersion of nanorods in pyridine and aerosols for the uniform film casting and large charge transfer interface with P3HT to reduce the exciton recombination system weight 33 1245819 发明, description of the invention. Because the structure of the solar cell allows the electric field to extend across the thickness of the device rather than on a plane, it is also important to describe the cross-sectional shape of the blend film. To accomplish this, a solution of 60% by weight of 10 nm X 10 5 nm CdSe nanocrystals in P3HT was spin-coated from the solution on Polybed epoxy discs. The disc was then micro-cut with a diamond knife to produce a 60 nm thick film. These ultra-thin films contain a nanocrystalline-P3HT cross section at one edge. In the TEM image of the film, Figure 14, the dark section without nanocrystals is an epoxy material, and a P3HT film containing nanocrystals can be seen on it, spinning 100 10 nm wide. Nanocrystals evenly span the entire film thickness without significant phase separation in the lateral direction. Obtaining a long nanorod-polymer film cross-section system is very difficult. Nanorods are resistant to cutting due to their large size, and the blend film has a tendency to tear and be dragged by a cutter. Therefore, once the film is rotated on the epoxy disc, it is buried in the epoxy for 15 days and cured to provide further support during microdissection. The cross section formed by 40% by weight of 7 nm X 60 nm CdSe nanorods in P3HT shows that the nanorods span most of the film thickness, Figure 15b. As the length of nanorods increases to span the thickness of photovoltaic devices, 20 electron transport is expected to be substantially improved. However, the improvement expected for shipping assumes that the nanorods are aligned perpendicular to the plane of the substrate and that they are long enough to allow the electrons to be fully transported within a nanorod. Figure 15 shows that nanometer particles are randomly dispersed, but some particles are oriented with major components in the direction of electron transport. Further evidence of the arrangement of the nanorods and their beneficial effects on electron transport can be observed in light 34 1245819, Invention Description Current. As long as the following quantities can be compared for a group of devices, EQE can be used as a charge transport, (iii) the charge collection efficiency at the electrode (which is mainly selected by the electrode), and the 5V charge transfer efficiency (self-induced quenching termination) Decide). Which data, as shown in Figure μ, the device meets these four conditions. Therefore, we concluded that when the aspect ratio of the nanorods was increased from i to 10, Figure 17, the charge transport needs to be significantly improved to produce an Eqe improvement of the factor of 3. In a network of shorter nano-particles, the electron transport is controlled by the beating of individual particles (which is controlled by a circuit containing an electrode that collects electrons 10. However, in a device composed of larger particles, f Band conduction is common, because the path can be formed from a single nanorod. Because the nanorod in the device. The thickness of the polymer film is about · nm, and a 60 nm long nanorod can pass through a significant part of the device Passed through, and the particles with a length of 30 and 7 nm are progressively less effective, Figure 16. The best device 15 (which contains 7 nm X 60 nm nanorods) is exposed to 0 ″ mWW at 485 nm. Performed at a maximum of 55%, and this value is significantly renewable. The reported results are presented in individual cases in five sets of devices made from three different CdSe synthetic batches (a total of 57 individual solar cells) The median value of the maximum external quantum efficiency of each of these 57 devices is within 10% relative to the median value, and the highest obtained efficiency is 59%, all of which are in the range of ~ (U mW / cm2 Monochromatic illumination. Individual devices have been repeatedly described over several months. And it shows no weight change between measurements. Because of the superior carrier transport properties of inorganic semiconductor nanorods compared to semiconducting organic polymers and J-knives, these hybrid nanorods_Polymer 35 1245819 玖, Description of the invention Solar cells are implemented with the highest EQE under low-intensity irradiation, which is reported for polymer-containing batteries to date. The considered device is a photovoltaic device according to the invention incorporated into a highly branched nanorod. Nanorods are synthesized from 5-10 precursor injections according to techniques known in the art. During subsequent injections during the synthesis, these nanorods developed many nucleation sites for branching and increasing length. Because Many of these branched nanorods have lengths greater than 100 nm, and a further increase in EQE is expected to be used in nanorod-polymer PV devices. The branching is through the fiber-zincite structure of the rod. Low energy sphalerite loss (series 10 is similar to the lack of lamination defects, which results in nanorods having kinks along their length). Therefore, the carrier mobility in branched nanorods is expected It is similar to unbranched rods. Furthermore, the interaction between the branch and the body of the nanorod is stronger than that between two individual nanorods in physical contact. Therefore, the ribbon is transported in the branched nanorod. It is common, and the electronic beat occurs between individual nanometer 15-meter rods. It should be understood that the embodiments of the present invention include nano-crystalline particles with more complex shapes. In the embodiment of the present invention, the initial nucleation results in a core with a cubic crystal structure. (Eg, sphalerite crystal structure). Subsequently, an arm with a hexagonal crystal structure (eg, fiber zincite) can emerge from the core. However, different growth 20 conditions can be provided to statistically alternate to form cubes and six The angular crystal structure, therefore, leads to irregular branches. Sequential branching of "inorganic dendrimers" can be generated by precise temperature control throughout the reaction, see Mana et al. 1 XM · C / zem · S% ·, 2000, 122, 12700-2706 and US Serial No. 10/301, Case No. 510 (application on November 20, 2002, currently under trial). 36 1245819 发明, description of the invention The inherent nature of a tetrapod with an arm that always points to an electrode and combined with a low band gap material (such as CdTe), arranged on the substrate, is buried in the conjugated polymer The tetrapod semiconductor-nanocrystal becomes a particularly preferred embodiment. Compared with the nanocrystalline particles with arbitrary orientation, the tetrapod according to the embodiment of the present invention is arranged and can provide a current path in a single direction than the nanocrystalline particles with arbitrary orientation. The photocurrent spectra of 90% by weight CdSe branched nanorod blends in P3HT for various pyridine concentrations are shown in FIG. The preferred pyridine concentration for branched nanorods occurs at 12%, which is significantly higher than the shorter 10 unbranched rods, which is 8% or less. The maximum EQE for these devices is 31% at 450 nm at approximately 0.1 mW / cm2. Contrary to expectations, this EQE is almost a factor 2 lower than that of devices made from 60 nm nanometers. The dispersion of longer nanorods (> 100 nm) in P3HT is limited by its solubility in pyridine-chloroform. When the branched nanorods are dissolved in pyridine-chloroform, it forms a gelatinous viscous solution. This indicates the lower solubility of branched bodies and the higher nanorod-nanorod interactions relative to the nanorod-solvent interaction. With these branched objects, the CdSe-P3HT film is cast with uneven and scattered light, which clearly indicates giant phase separation. Any improvement in transport efficiency is aggravated by a decrease in charge separation efficiency, which is caused by a reduction in the area of the interface between the nanorod and 20 P3HT. Long cadmium selenide nanorods in high-concentration solutions that are passivated with pyridine are separated by a small distance, and in some cases the diameter of pyridine. At this close distance, the attractiveness of Van der Waals (which increases and decreases with volume and distance) is very strong and promotes aggregation. Dissolving high-concentration long nanorods, which are necessary for the manufacture of films with sufficient thickness for PV devices 37 1245819 (invention description), is a challenge. Coordination systems with larger sizes and longer chains are necessary to extend the length of nanorods added to the polymer. In order to avoid such ligands from acting as barrier layers, they need to be electrically active and energy levels need to facilitate the charge transfer between CdSe and P3HT. 5 The complete strip conduction of electrons requires that the entire transport be contained within a single nanocrystal. Further improvements in shipping are based on the arrangement of nanorods in film thickness. Nanorod alignment methods include electric fields and stretch alignments, both of which require significant improvements in the processing and structure of the current device. The tetrapod (having four identical arms attached to the center of the cube) is oriented so that it naturally aligns on the surface, with one arm 10 perpendicular to the plane of the substrate, as seen in Figure 19. Therefore, the hybrid solar cells produced next can be incorporated into tetrapods as self-aligned nanocrystals to efficiently transport electrons. Another embodiment of the present invention is to operate the nanorod / polymer photovoltaic device of the present invention at an astonishing film thickness. One of the many advantages of using nanocrystalline and poly15 compounds is the high absorption coefficient compared to bulk inorganic semiconductors. This results in a thin film, typically less than 300 nm, which can absorb more than 90% of incident radiation. Unlike traditional inorganic semiconductor solar cells, which require more than a few microns in thickness to absorb light, low-material use and flexible devices are possible with nanocrystalline and polymer systems. Although it is not intended to be limited by any particular theory or mechanism, it may be due to the good transport properties of the nanorods that can be used when the length of the nanorods spans a significant portion of the film. The efficiency and film of the nanorod-polymer PV device The thickness dependence provides further information on the nature of the carrier transport. The photocurrent spectrum of the above-mentioned device for examining absorption is as shown in Fig. 20, 1245819 (20) and the description of the invention. When the thickness of the film is increased from 100 nm to 350 nm, the corresponding increase in EQE and its subsequent decrease are not only caused by the increase of absorbed light. The spectral shape depends on the thickness of the device, and the light response in the red region of the spectrum is increased by the thicker film. This can be attributed to the weak filtering effect, which was generated from the 5 parts of the film that did not cause photocurrent. Because in a thick film, compared to the transport contained in a single particle, the nanorod network in physical contact transports electrons with low carrier mobility, and the electrons generated near the PEDOT: pss electrode need to be used. Many nanorods traverse to the collecting aluminum electrode. Blue light, which is absorbed closer to the transparent electrode, does not contribute strongly to photocurrent. In addition, the electric field on the device associated with causing charge separation is a reduction in the specific bias voltage of the thicker film compared to the thinner film. The author has surprisingly found that nanorod-polymer devices are made significantly thicker (200 nm) to achieve more light absorption, because the dispersion characteristics of nanorods are well controlled and the transport properties of nanorods are comparable. The organic material is more effective. The photocurrent spectrum of a device with 90% by weight of 7 nm spherical nanocrystals in P3HT exhibits similar properties, Figure 21a. The absorption spectrum of this group of devices with varying thickness is shown in Figure 21b. As the thickness of the device increases, EQE (which is a function of wavelength) shows a more significant 20 response in the red region of the spectrum. For these spherical nanocrystals, the optimum device thickness is 160 nm, which can be compared with the optimum value of 212 for long nanodevices. Because long nanorods show improved electronic transport compared to shorter spheres, the device can be made thicker to absorb more light before it begins to be dominated by beating transport. This further provides evidence of the benefits of using nano-rods with a degree of space to improve the delivery. 39 1245819 发明 Description of the invention In another embodiment of the present invention, a photovoltaic device is disclosed here, which is integrated on the top of the ITO electrode. PEDOT: PSS (poly (ethylene-dioxy) thiophene: poly (styrenesulfonic acid)) electron hole transport layer. The incorporation of an electron hole conducting layer on top of the ITO electrode 5 (PEDOT / PSS) produces several beneficial effects, including, for example, providing a smoother surface, and depositing a nanocomposite layer on it by, for example, spin casting. Moreover, its work function conforms better to the valence band of the conductive polymer (P3HT) than ITO, thereby promoting the conduction of the electron hole. Of course, various electron hole conducting layers can be selected according to the work function of the electrode material used. A non-limiting example of this device is shown in Figure 4. The preferred embodiment of the present invention is a 90% by weight solution of 7 nm X 60 nm CdSe nanorods in P3HT, which is cast on a PEDOT: PSS coating (with aluminum as the top contact). A semiconductor nanocrystalline polymer Fangyang energy 15 cell constructed on an ITO glass substrate. The power conversion efficiency of 6.9% was obtained in an inert atmosphere of flowing argon at 515 nm and 0.1 mW / cm2. At this intensity, the open-circuit voltage is 0.5V, the photovoltage at the maximum power point is 0.4V, and the fill factor is 0.6, Figure 23a. For plastic PV installations, this monochrome power conversion efficiency is one of the highest reported. Very few polymer-based solar cells can achieve monochromatic power conversion efficiencies above 2%. The most reliable example is the soluble derivative of C60 and the blend of MEH-PPV, which has an efficiency of 5%. In another embodiment of the present invention, the arrangement of the semiconductor-nanocrystals in the thickness of the film can be further controlled by external assistance. Arrangement aids may include those that are familiar to those skilled in the art. These systems include an aid that can generate electrical, magnetic, or stretched alignments that can be used to arrange nanocrystals. For the purposes of the present invention, the arrangement can be defined if the nanocrystals between 10 and 99% have their longitudinal axis (which is aligned by not more than 20 degrees perpendicular to the film surface). 5 Experiments The above description has several embodiments of the invention detailed herein. Some parameters of the above embodiments are summarized in Table 1. Further non-limiting examples of the invention are detailed below. Pyr / Chlor is a pyridine in a chloroform mixture. 10 Table 1 Nano crystal load, weight% Nano crystal size, nm Nano crystal material / polymer solvent mixture solvent content, vol% Reference 90 7x7 CdSe / P3HT Pyr / chlor 100 Figure 4 90 9x 13 CdSe / P3HT Pyr / chlor 0-20 Fig. 6 90 3x 100 CdSe / P3HT Pyr / chlor 12 90 7x60 CdSe / P3HT Pyr / chlor 4 0-95 3x60 CdSe / P3HT Pyr / chlor Fig. 8 10 60 10x 10 CdSe / P3HT Pyr / chlor Figure 14 7x60 CdSe / P3HT Pyr / chlor Figure 15 Nanocrystals are mainly composed of trioctylphosphine oxide (TOP0) and tributyl- or trioctylphosphine and a small amount of various phosphonic acids The composition is composed of a mixture and synthesized by techniques known in the art using organometallic precursor pyrolysis, see Peng et al. TVa / wre 2000, 404, 59; and Peng et al. 15 d 777. C / zem. aSoc. 2001, 123, 1389. The recovered product was dispersed and washed three times in methanol to remove excess surfactant. Pyridine treatment of nanocrystals to remove surfactants used in nanorod synthesis is accomplished by dissolving the particles in pyridine and then precipitating in hexane. Although coated with TOP0

41 1245819 发明, description of the invention

CdSe nanocrystals are soluble in hexane, but pyridine-coated particles are insoluble in hexane. Repeating the pyridine treatment two to three times can effectively replace more than 95% of TOPO on the nanocrystalline surface.

The CdTe quadruped system is synthesized as described in US Serial No. 10 / 301,510 (filed on May 20, 2002, currently under trial), which is essentially as described below. Cadmium oxide (CdO) (99.99 +%), tellurium (Te) (99.8%, 200 mesh) and tri-n-octylphosphine oxide (C24H510P or TOPO, 99%) were purchased from Aldrich. N-octadecylphosphonic acid (C18H3903P or ODPA, 99%) was purchased from Oryza Laboratories, Inc. Trioctylphosphine (TOP) (90%) was purchased from 10 Fluka. All solvents used were anhydrous, purchased from Aldrich, and used without any further purification. All operations are performed using standard coated space-free technology. The molar ratio of Cd / Te varies from 1: 1 to 5: 1, and the molar ratio of Cd / ODPA varies from 1: 2 to 1: 5. The precursor solution was prepared by dissolving tellurium powder in TOP (Te concentration 10% by weight). The mixture was stirred at 25 ° C for 15 minutes and then cooled and centrifuged to remove any remaining insoluble particles. In a typical CdTe tetrapod synthesis, a mixture of OdPA, TOPO and CdO was degassed in a 50 ml three-necked flask connected to a Liebig condenser at 120 ° C for 20 minutes. Slowly heat at Ai · until CdO decomposes and the solution becomes clear and colorless. Second, ι. 5 grams of trioctylphosphine 20 (TOP) was added, and the temperature further rose to 320 ° C. Thereafter, the Te: TOP precursor solution was rapidly injected. The temperature dropped to 3 15dc and was maintained at this value throughout the synthesis. All synthesis was stopped after 5 minutes by removing the heating mantle and by rapidly cooling the flask. After the solution was cooled to 70 ° C, 3-4 liters of anhydrous xylene was added to the calciner, and the dispersion was transferred to an Ar dry 42 1245819 玖, invention description box. A minimum amount of anhydrous methanol, which is used to precipitate nanocrystalline particles after centrifugation, is added to the dispersion. In this way, the possible co-precipitation of Cd-phosphonate complexes is avoided. After the upper layer was removed, the precipitate was redissolved twice in methanol and precipitated again with methanol. After the upper layer is removed, the final precipitate 5 is stored in a dry box. All CdTe tetrapods formed are easily soluble in solvents such as chloroform or toluene. Example 1 = According to an embodiment of the present invention, a photovoltaic device is spin-cast from a solution of CdSe nanocrystals and P3HT in a pyridine-chloroform solvent mixture on an ITO-coated glass substrate in an inert atmosphere. It was prepared by pumping at < 10 · 10 6 mbar for 12 hours and evaporating the aluminum on the top to obtain the structure shown in FIG. 2. Example 2: a. Synthesis of nanocrystals: According to another embodiment of the present invention, the long CdSe nanorods (90% by weight) in P3HT were synthesized as follows: Cd raw material ... 0.161 g of dimethyl Cadmium was dissolved in 0.34 grams of trioctyl 15 phosphine (TOP). Se raw material: 0.2 g of Se in 2.367 g of TOP is dissolved. In a three-necked flask, 3.536 grams of trioctylphosphine oxide (TOPO), 0.187 grams of hexylphosphonic acid (HPA), and 0.357 grams of tetradecylphosphonic acid (TDPA) were mixed. This mixture was heated and degassed to 360 ° C under argon. The Cd raw material was slowly injected. Then, the temperature dropped to 330 ° C, and the Se raw material was injected at a rapid rate. The reaction was performed at 290 ° C for 18 minutes, and then the heat was removed. At 40 ° C, about 15 ml of methanol was added to the flask. The mixture was subjected to centrifugation and the supernatant was discarded. 8 ml of methanol was added, vortexed, then centrifuged again, and the upper layer was discarded. b. Preparation of substrate: In a series of solvents, the glass is cleaned by sonication. 43 1245819 玖, description of the invention Indium osmium oxide (ITO) on the glass substrate. After the final solvent cleaning, the mold is dried and embedded in a previously cleaned plasma chamber. Face down samples were treated with plasma for 4 minutes. Once the sample was removed from the chamber, precipitation of PEDOT: PSS (available from Bayer-Electronic Grade) began. After filtering through a 0.2 micron acetic acid filter, PEDOLPSS was deposited by spin casting at 3000 rpm. The film was dried by heating at 120 ° C for one hour under flowing argon. c. Cleaning of nano crystals: Cut the synthesized nano rods in half, and add 8 ml of methanol to each half. Perform centrifugation and discard the upper layer, and then repeat this process again. Add 0.35 ml of pyridine to each half to dissolve the nanorods, heat at 120 ° C and vortex occasionally for 10 minutes. Take 8 ml of each half of Shen Dian. Perform centrifugation and discard the upper layer. The nanorod was dissolved in a chloroform-pyridine mixture with 9.2% pyridine to produce nanocrystals at a concentration of 83 mg / ml. 15 d. Deposition of the active layer: The regular poly (3-hexylthiothiophene) (P3HT) was dissolved in chloroform at 30 mg / ml. A common solution of nanorods and P3HT prepared in a chloroform / pyridine mixture using this solution and the above nanorod solution (see III above), having a mass ratio of 9: 1 nanorod to P3HT and 4.55 mg / ml P3HT concentration. From this solution, the film was spin-cast on the prepared substrate (see above II) at 20 1350 rpm. e. Electrode deposition: Load the sample into the evaporation chamber and pump it under vacuum for at least 8 hours to a pressure below 10.6 Torr. A thin film of about 100 nm thick is thermally deposited through a shadow mask to define the top electrode. 441245819 发明, Inventive Example 3: CdTe tetrapod in P3HT has a core and 4 branches. CdTe tetrapod nanocrystals with 80 nm arm were synthesized and then washed in tetrahydrofuran (THF) and ethyl acetate in several dissolution / precipitation steps. 5 Then, the nanocrystals are dissolved together with the ligand phenylphosphonic acid in the solvent chloroform and heated at about 100 ° C for several hours. Nanocrystals were then precipitated with methanol and redissolved in chloroform. As described in Example 2, the nanocrystalline solution and the P3HT solution were mixed and spin-cast to produce a thin film. 10 The substrate and electrode are treated as in Example 2. The EQE value of this sample is less than 10%. Example 4: CdTe tetrapod in P3HT

CdTe tetrapods were synthesized and washed with toluene and methanol as in Example 3 (which is based on THF and ethyl acetate). 15 Nanocrystals (about 50 mg) were then dissolved together with about 1,000 mg of the ligand hexylphosphonic acid (HPA) in about 2 ml of chloroform and heated for several hours. The rest of the procedures follow Example 3. The EQE value of this sample is less than 10%. Example 5: CdTe tetrapod in P3HT was performed as in Example 4, but nanocrystals were dissolved in tributylphosphine (TBP) and stirred for 20 hours before precipitating with methanol. Then, proceed as in Example 3. The EQE value of this sample is less than 10%. Example 6: CdTe tetrapod in MEH-PPV was performed as in Example 3, but was dissolved again in the solvent p-diphenylbenzene after the final methanol precipitation. Therefore, this example has the ligand phenylphosphonic acid. 45 1245819 发明, description of the invention MEE-PPV solution prepared in p-xylene, this was mixed with nanocrystals, and this was cast and mixed into a film as in Example 2. Example 7: CdSe nanorods in P3HT Perform as in Example 2, but the ligand pyridine can be replaced with n-butyl 5 amine or n-hexylamine in each step. Example 8: CdSe nanorods in P3HT proceed as in Example 4, but CdTe nanocrystals are replaced with CdSe nanocrystals. Moreover, TPA substitutes T1 as a ligand. Example 9: CdSe or CdTe nanocrystals in PBS 3 10 CdSe or CdTe nanocrystals were processed as in Example 8. Replace TPA with T5-PA. The quality, shape, and structure of nanocrystals were determined by TEI and using a FEI Tecnai 12 120kV microscope. A film of a blend of CdSe-15 P3HT (Regularly Regular P3HT of Alddch) of about 50-100 nm thickness is made by casting the film in a NaCl IR window, floating the film in water and collecting it with a copper TEM grid. Study using TEM. The morphology of the blend film was also directly identified on the device via atomic force microscopy using Digital Instruments' Nanoscope IIIa in tapping mode. Thin 20 film thickness is determined via AFM.

The absorption of CdSe-P3HT blend film is determined by the ultraviolet / visible spectrophotometer of Agilent Chemstation. The photocurrent measurement is performed using a 250-watt tungsten light source (which is coupled to an Acton SP150 monochromator as an illumination source and a Keithley 23 6 46 1245819 (source description measurement unit) for obtaining current and voltage). Light intensity is measured with a calibrated Graseby light-diode. The photoluminescence quenching experiment was performed on a 100-200 nm-thick CdSe_p3HT film cast on a glass substrate. The absolute photoluminescence of the sample under the excitation of 514 5 nm from the argon ion laser was measured with an integrated sphere in accordance with the method of deMello et al. As described in 1997, 9, 23 °. The efficiency of photovoltaic devices can be described in two ways, see Rostalski Female /. 6W. Heart / Heart / 61,87 (200) (the content of which is hereby incorporated by reference in its entirety for reference) . The first kind of coefficient quantity efficiency, external quantum efficiency (EQE), represents the number of photons that are converted into electrons. The second is the power conversion efficiency, which represents the electricity generated by each unit of incident radiant power. Although EQE is important for understanding the current generating mechanism, it is only measuring the efficiency of commercial solar current. More important for these commercial installations is the power conversion efficiency of this installation under solar conditions. For commercial applications, the most important parameter is the power conversion efficiency of photovoltaic cells77. Because power is the product of current and voltage, power conversion efficiency is determined by the current (which is a function of voltage). Power conversion efficiency can the battery enter the light power?丨 _ and electrical output power Pout means:

The maximum theoretical power output of 2 AM is expressed by the product of short circuit (shon circuit) photocurrent 4 and open circuit current [F ~. Figure 24 shows the ideal and experimentally found typical I-V curve. The area of the inner shape corresponds to 47 1245819 of the actual device. Description of the invention The maximum output power (at the maximum power point), while the area of the outer rectangle formed by the axis and the ideal I-V curve is equal to the maximum ideal output power. The actual I-V characteristics are plotted, and the product of current and voltage needs to be maximized in order to obtain the maximum power output. The ratio of the maximum theoretical power output to the actual maximum power output is an important feature of the LV characteristic description. This ratio is called the fill factor FF, and can be defined as —λ⑼ ⑻ ⑻ — the right uses the fill factor to represent the maximum output power of photovoltaic cells, and the power conversion efficiency becomes 10 W) Big 5 Gongxun is included in the IV characteristics of the device Within the description. It is proportional to QE and combined with d c and FF, provides all the parameters needed to describe the power efficiency characteristics of the battery. The present invention considers that the photovoltaic battery described here has a power conversion efficiency of more than 1% A.M · 15 full irradiation. More preferably, this content is greater than 5%. More preferably, the content is greater than 10%. Optimally, this content is up to 30%.

Power conversion efficiency can be generated under monochromatic or white light. Monochromatic power conversion efficiency is not sufficient to describe the characteristics of solar cells, but it is a measure of device performance at a specific wavelength. This is useful when the device is used in conditions other than the sun, such as small electronic devices and watches used in the ambient room light, and power meters for laser radiation. Describing Matt 48 1245819 发明 Description of the invention The standard method for the characteristics of a solar cell is the Air Mass 1.5 or A.M. 1.5 conditions (the solar emission spectrum after the Earth's atmosphere travels 1.5 times). This solar exposure is generally simulated because standard A.M. 1.5 conditions are difficult to obtain reliably due to non-ideal climatic conditions. 5 The terms and expressions used herein are for description, not limitation, and the use of these terms and expressions is not intended to exclude the illustrated or described features or equivalents of parts thereof. It is understood that various modifications are possible within the scope of the claimed invention. Furthermore, without departing from the scope of the invention, any one or more features of any embodiment of the invention may be combined with any one or more other features of any other embodiment of the invention. All the patents, patent applications and announcements mentioned above are incorporated herein for all purposes. None of the above patents, patent applications, and announcements are considered to be know-how. Brief description of t diagram 3 15 The first diagram shows the energy level diagram of CdSe and P3HT, which shows 5 nm

Schematic diagram of the charge transfer method between CdSe and P3HT. Figure 2 is a schematic diagram of the structure of a nanorod-polymer blend photovoltaic device according to an embodiment of the present invention. Figure 3 shows low-resolution TEM images of a) 7 nm X 7 nm, b) 8 nm X 13 nm, c) 3 nm 20 x 60 nm, and d) 7 nm x 60 nm CdSe nanocrystals. Figure 4 shows the AFM-TM morphology image of a thin film (rotated from chloroform) composed of 90% by weight of 7 nm x 7 nm CdSe nanocrystals dispersed in P3HT. The scanning area is 5 // m. 49 1245819 发明, description of the invention Figure 5 shows a film composed of 90% by weight of 9 nm X 13 nm CdSe nanocrystals dispersed in P3HT (from 1% by volume and 8% by volume of pyridine in chloroform) AFM-TM a) morphological image and b) phase image. The image is presented in a 5 // m scan area with the same specifications. 5 Figure 6 shows the surface roughness (hollow circles) of a film consisting of 90% by weight of 9 nm X 13 nm CdSe nanorods (cast from various concentrations of pyridine in chloroform) dispersed in P3HT. Maximum EQE (Solid Diamond Shape) is shown with devices made from these films. The line acts as a guide for the eyes. Figure 7a shows the normalized photocurrent of a device (hollow circle) in 90% by weight 3 nm X 60 nm CdSe nanometer 10-meter rod in P3HT (annealing) at 120 ° C spectrum. Figure 7b shows the ratio of EQE before and after heat treatment of a 90 nm by weight 3 nm X 60 nm CdSe nanorod device and a nanorod only device in P3HT as a function of wavelength. The insertion plot shows individual 1-transmission spectra of CdSe and P3HT at 3 nm X 60 15 nm. Figure 8 shows the P3HT pair absorption (solid diamond shape, dotted line), photocurrent (open circle, solid line), P3HT pair absorption of various 3 nm x 60 nm nano rod devices of various series of nano rod concentrations in P3HT, and Relative benefit of photocurrent (solid distance, dotted line) after heat treatment at 120 ° C. 20 Figure 9 shows 90% by weight of 7 nm X 14 nm CdSe EQE in P3HT under -0.1 mW / cm2 at 515 nm. Insertion plots show the PL efficiencies of 60 wt% 7 nm X 14 nm CdSe in a P3HT sample under 514 nm excitation after heat treatment at various temperatures. Figure 10 shows EQE spectra of 90 wt% 7 nm X 60 nm CdSe nanorods at 50 1245819 玖, description of invention P3HT (open circles) and heat treatment at 120 ° C (solid distance shape). Insertion diagram: The corresponding current-voltage characteristics of this device under 515 nm Risi 0 · lmW / cm2 irradiation, which includes an open circuit voltage of 0.4V and a fill factor of 0.5. 5 Figure 11a shows the EQ0 spectra of 90% by weight 7 nm X 60 nm CdSe nanorods with a thickness of 212 nm, 271 nm, and 346 nm from P3HT before heat treatment at 120 ° C. The lib graph shows the EQ0 spectrum of a 90% by weight 7 nm X 60 nm CdSe nanorod device with a thickness of 212 nm, 271 nm, and 346 nm from P3HT 10 after heat treatment at 120 ° C. Figure 12a shows the relative promotion of EQE before and after heating of the device of Figure 11a and lib. Figure 12b shows the absolute difference in EQE before and after heat treatment. Figure 13a shows 20% by weight of 3% by weight of the rotatory casting of chloroform. TEM of nm X 60 15 nm CdSe nanorods and thin films of P3HT. Figure 13b shows the same nanocrystals of Figure 13a from TEM when 10% by volume of pyridine was cast in a chloroform solution. Figure 14 shows due to P3HT The TEM of a cross section of a 100 nm thin film consisting of 10 nm X 10 nm CdSe nanocrystals within 60% by weight. Figure 15a shows the 7 nm X 60 nm CdSe nanorod. Figure 15b shows the TEM of a 100 nm thin film composed of 40% by weight CdSe nanorods. Figure 16 shows that the length of a 7 nm diameter nanorod is continuously illuminated from 0.084 mW / cm2 at 515 nm from 7 nm Increasing to 30 nm and 60 51 1245819 发明, invention description nm, for the EQE of the device with 90% by weight in 0% of P3HT, it increased to a factor of 3 to 54%. Figures 17a-c shows a) TEM of 7 nm, b) 30 nm and c) 60 run diameter 7 nm diameter nanocrystalline. The scale setting is 50 nm, 5 and all TEM systems are the same scale. Fig. 18 shows the EQE of a device of 90% by weight of a 3 nm X 100 nm branched CdSe nanorod in P3HT as a function of pyridine concentration. Figure 19a shows the unaligned tetrapod nanocrystals. 10 Figure 19b shows nanocrystals of aligned tetrapods. Figure 20 shows the EQE spectra of a series of devices with different film thicknesses of 90% by weight of 7nm X 60 nm CdSe in P3HT. Figure 21a shows the EQE spectra of 7 nm X 7 nm CdSe at 90% by weight in P3HT for various film thicknesses. 15 Figure 21b shows the corresponding absorption spectra of these devices as a function of increasing thickness. Figure 22a shows a TEM of 40% by weight of 5 nm CdSe nanocrystals treated with TOPO-treated nanocrystals in P3HT. Figure 22b shows a TEM of 40 20 wt% 5 nm CdSe nanocrystals of T1 treated nanocrystals crystallized in P3HT. Figure 22c shows a TEM of 40 wt% 5 nm CdSe nanocrystals of pyridine-treated nanocrystals in P3HT. Figure 23a shows the I-V characteristics of a 90% by weight 7 nm X 60 nm CdSe nanorod in P3HT at 5 1 5 nm at 0.1 mW / cm2. 52 1245819 发明, Description of the invention Figure 23b shows the characteristics of the solar cell of the same device shown in Figure 23a. It is measured with an analog AM 1.5 Global light source, including a short circuit current of 5.7 mA / cm2, a FF of 0.42, and a 0.67V. The open-circuit voltage produces a solar power conversion efficiency of 1.7%.

5 Figure 24 shows the I-V curve of the physical phase and the typical I-V curve found experimentally. 53

Claims (1)

1245819 Patent application scope Patent Application No. 92106081 Patent Application Amendment to Patent Scope June 10, 19941. A thin film comprising: a semiconducting conjugated polymer having at least 5% by weight of semiconductor-nanocrystals buried therein, Wherein, at least a part of the semiconductor-nanocrystal has an aspect ratio greater than about 2. 2. The film according to item 1 of the scope of patent application, wherein: at least a part of the semi-V-body-nanocrystal has an aspect ratio greater than about 5. 10 3. The thin film according to item 1 of the scope of patent application, wherein: at least a part of the semiconductor-nanocrystal has an aspect ratio greater than about 10. 4. The thin film according to item 1 of the scope of the patent application, wherein: at least a part of the semiconductor-nanocrystal has an aspect ratio of about 5 to about 50. 5. The thin film according to item 丨 of the patent application scope, wherein: at least a part of the semiconductor-nano crystal has an aspect ratio between about 2 and about 10. 6.  The film according to item 1 of the scope of the patent application, wherein: ′ The semiconducting polymer has about 5 to about 99% by weight of semiconductor-nanocrystalline crystals buried therein. 7.  The thin film described in item 1 of the scope of the patent application, wherein the semiconductor polymer has approximately 20 and 95% by weight of semiconductor-nanocrystalline crystals buried therein. 1245819 Patent application scope 8.  The film according to item 1 of the patent application range, wherein: the semiconducting conjugated polymer has about 50 and 95% by weight of semiconductor-nanocrystals buried therein. 9.  The film as described in the item of the scope of the patent application, wherein: 5 the semiconductive conjugated polymer has approximately 90% by weight of semiconductor-nanocrystals buried therein. 10. The film according to item i in the scope of the patent application, wherein: the semiconductive conjugated polymer is selected from the group consisting of trans-polyacetylene, polypyrrole, polythiophene, polyaniline, and poly (p-phenylene) And poly (p-phenylene_ethenyl) 10, polygo, polyaromatic amine, poly (hexyl · ethylene) and its soluble derivatives. 11 · The film according to item 丨 0 of the patent application scope, wherein: the conjugated polymer is selected from (poly (2-methoxy 5_ (2, _ethylhexyloxy) p-phenylene vinylene ) (MEH_PPV) and poly (3-hexylthiophene) (p3HT) m 15. 12.  The thin film as described in item 1 of the patent application scope, wherein: 3 semiconductor-nanocrystals include rods having a length greater than about 20 nm. 13.  The film as described in the scope of the patent application, wherein: The Hei semiconductor-nano crystal contains a rod having a length of 20 degrees between about 20 nm and about 200 nm. 14. The thin film according to item 13 of the scope of the patent application, wherein the semiconductor-nanocrystal contains a rod having a length between about 60 and about 110. 15. The thin film described in item 1 of the scope of patent application, wherein 1245819, the scope of patent application The semi-V-body-nanocrystal contains a rod of about 7 nm x go nm. 16. The thin film according to item 1 of the scope of the patent application, wherein: the semi-'body-nano crystal comprises a semiconductor selected from the group consisting of a semiconductor of a family, a family, a family, and a tertiary mica copper ore. 17. The thin film according to item 16 of the scope of the patent application, wherein: the semiconductor-nano crystal system is selected from the group consisting of CdSe, CdTe, InP, GaAs, CuInS2, CuInSe2, A1GaAs, osmium, Ge & si. 18. The film according to item i in the scope of the patent application, wherein: the semiconductor-nano crystal system is selected from the group consisting of CdSe & CdTe. 19 · The film according to item i in the scope of patent application, wherein: Part of the semiconductor-nanocrystal is a branched nanocrystal. 20. The film as described in item 19 of the Shenjing patent scope, wherein: a part of the knife-shaped nanocrystal has at least two arms, and the arms are not all the same length. 21 · The film according to item 19 of the scope of patent application, wherein: the branched nanocrystals all have the same shape. 22. The film according to item 19 in the scope of patent application, wherein: the branched nanocrystal has four arms and has tetrahedral symmetry. 23. The thin film according to item 22 of the scope of patent application, wherein: dagger-like nanocrystalline CdSe or CdTe is buried, and is embedded in an amount of about 90% by weight. 24. The film according to item 1 of the scope of patent application, wherein: Ϊ245819, patent application scope The film has a thickness of about 100 nm to about 350 nm. 25. The thin film according to item 22 of the scope of patent application, wherein: the far film has a thickness of about 200 nm. 26. A photovoltaic device comprising: 5 The film according to item 1 of the scope of patent application. 27. The photovoltaic device according to item 26 of the scope of the patent application, wherein at least a portion of the semiconductor-nanocrystal has an aspect ratio greater than about 5. 28. The photovoltaic device according to item 26 of the scope of the patent application, wherein: at least a part of the semiconductor-nanocrystal has an aspect ratio greater than about 〇. 29. The photovoltaic device according to item 26 of the Shen Qing patent scope, wherein: at least a part of the semiconductor-nano crystal has an aspect ratio between about 5 and about 50. 15 30. The photovoltaic device according to item 26 of the scope of the patent application, wherein: at least a part of the semiconductor-naira crystal has an aspect ratio between about 2 and about 10. 31. The photovoltaic device according to item 26 of the scope of the patent application, wherein: the semiconductive conjugated polymer has about 5 and about 99% by weight of semiconductor-nano crystals buried therein. 32. The photovoltaic device according to item 26 of the scope of the patent application, wherein: the semiconducting conjugated polymer has approximately 20 and 95% by weight of semiconductor-nanocrystals embedded therein. 33. The photovoltaic device according to item 26 of the scope of patent application, wherein: 1245819 The scope of patent application This semiconducting co-polymer has about 50 and 95% by weight of the semiconductor buried in it. Rice crystals. 34_ The photovoltaic device according to item 26 of the scope of patent application, wherein: the semiconducting polymer has approximately 90% by weight of a semiconductor-nanocrystal buried therein. 35. The photovoltaic device according to item 26 of the scope of application for a patent, wherein: the semiconductive conjugated polymer is selected from the group consisting of trans-polyacetylene, polypyrrole, polythiophene, polyaniline, poly (p-elongation Phenyl) and poly (p-phenylene-vinylidene), I, polyaromatic amine, poly (vinyl-vinylidene) and its soluble 10 derivatives. 36. The photovoltaic device according to item 35 of the scope of patent application, wherein: the conjugated polymer is selected from the group consisting of (poly (2-fluorenyloxy 5- (2, -ethylhexyloxy) -phenylene) Group consisting of vinylidene group (MEH-PPV) and poly (3-hexylthiophene) (p3HT). 15 37. The photovoltaic device according to item 26 of the scope of the patent application, wherein: the semiconductor-nanocrystal includes a rod having a length greater than about 20 nm. 38. The photovoltaic device according to item 26 of the scope of the patent application, wherein: the semiconductor semiconductor-nanocrystal includes a rod having a length between about 20 nm and about 200 nm. 20 39. The photovoltaic device according to item 38 of the scope of patent application, wherein: the semiconductor-nanocrystal includes a rod having a length between about 60 nm and about 110 nm. 40. The photovoltaic device according to item 26 of the patent application scope, wherein: the 5H semiconductor-nano crystal contains a rod of about 7 nm X 60 nm. 1245819 Scope of patent application 41.  The photovoltaic device according to item 26 of the scope of patent application, wherein: the semiconductor-nano crystal comprises a group selected from the group consisting of III-V, III-V, IV semiconductors, and tertiary mica copper ore Of semiconductors. 42.  The photovoltaic device according to item 41 of the scope of patent application, wherein the semiconductor-nano crystal system is selected from the group consisting of CdSe, CdTe, InP, GaAs, CuInS2, CuInSe2, AlGaAs, InGaAs, Ge, and Si. Ethnic group. 43.  The photovoltaic device as described in claim 26, wherein: the semiconductor-nano crystal system is selected from the group consisting of CdSe and CdTe 10 ° 44.  The photovoltaic device according to item 26 of the patent application scope, wherein: a part of the semiconductor-nano crystal is a branched nano crystal. 45.  The photovoltaic device according to item 44 of the scope of the patent application, wherein: a part of the branched nanocrystal has at least two arms, and the arms are not all the same length. 46.  The photovoltaic device according to item 44 of the patent application scope, wherein: the branched nanocrystals all have the same shape. 47.  The photovoltaic device according to item 44 of the patent application scope, wherein: the branched nanocrystal has four arms and has tetrahedral symmetry. 20 48. The photovoltaic device according to item 47 of the scope of the patent application, wherein: the branched nanocrystalline system is CdSe or CdTe, and is embedded in an amount of about 90% by weight. 49. The photovoltaic device according to item 26 of the application, wherein: the film has a thickness of about 100 nm to about 350 nm. 1245819 Patent application scope 50. The photovoltaic device according to item 49 of the patent application scope, wherein: the film has a thickness of about 200 nm. 51. A method for manufacturing a polymer film, comprising: washing a surfactant-coated semiconductor-nanocrystal at least 5 times with a solvent, and dissolving the cleaned semiconductor-nanocrystal and a semiconductive polymer together Yu Yiwu's cereal mixture, and the mixture is deposited, wherein at least a part of the semiconductor-nanocrystal has an aspect ratio of greater than about 2 to 10 in length. 52. The method for manufacturing a polymer film as described in claim 51 of the patent scope, wherein: at least a part of the semiconductor-nanocrystal has an aspect ratio greater than about 5. 15 53. The method for manufacturing a polymer film as described in item 51 of the scope of patent application, wherein: at least a part of the semiconductor-nanocrystal has an aspect ratio greater than about 丨 0. 54. The method for manufacturing a polymer film as described in item 51 of the scope of the patent application, 20 wherein: at least a part of the semiconductor-nanocrystal has an aspect ratio between about 5 and about 50. 55. The method for manufacturing a polymer film as described in item 51 of the scope of patent application, wherein: 1245819, the scope of patent application: At least the aspect ratio of the semiconductor-nanocrystal. The part has about 2 and about 10 56. As described in the 51st patent scope of the application, among which: the method of manufacturing a polymer film, the semiconducting conjugated polymer has a semiconductor-nanometer of about 5 and about crystallization. 99% by weight is buried therein. 5 The method for manufacturing a polymer film as described in item 51 of the patent #patent, where: the semiconducting conjugated polymer has about 20 and 95% by weight Within 10 semiconductor-nanocrystals. 58. The method for manufacturing a polymer film as described in claim 51 of the scope of patent application, wherein: the semiconducting conjugated polymer has approximately 50% and 95% by weight of semiconductor · nanocrystals embedded therein. 15 59. The method for manufacturing a polymer film according to item 51 of the scope of the patent application, wherein: the semiconductive conjugated polymer has about 90% by weight of semiconductor-nanocrystals buried therein. 60. The method for manufacturing a polymer film according to item 51 of the scope of the patent application, 20 wherein: the semiconductive conjugated polymer is selected from the group consisting of trans-polyacetylene, polypyrrole, polyfluorene, polyaniline, polyaniline (P-phenylene) and poly (p-phenylene-phenylene), polyfluorene, polyaromatic amines, poly (butylene-phenylene) and its soluble derivatives. 1245819 Patent application scope 61 · The method for manufacturing a polymer film as described in item 60 of the scope of patent application, wherein: the conjugated polymer is selected from (polymethoxy 5_ (2, -ethylhexyloxy) A group consisting of p-phenylene vinylene (KMEH-PPV) and poly (3-hexylthiophene) (P3HT). 62. The method for manufacturing a polymer film as described in claim 51 of the scope of patent application, wherein: the semiconductor-nanocrystal includes a rod having a length greater than about 20 nm. 63. The method for manufacturing a polymer film according to item 51 of the scope of the patent application, 10 wherein: the semi-v-body-nanocrystal includes a rod having a length between about 20 nm and about 200. 64. The method for manufacturing a polymer film as described in item 63 of Shen Qing's patent scope, wherein: the semiconductor-nanocrystal includes a rod having a length between about 60 nm and about 110. 65. The method for manufacturing a polymer film according to item 51 of the scope of the patent application, wherein: the semiconductor-nano crystal contains a rod of about 7 nm × 60 nm. 2066, The method for manufacturing a polymer film as described in item 51 of the scope of the patent application, wherein: 夂 ', the semiconductor_nano crystal comprises a + conductor selected from the ηνι family wealth family and a third-grade mica copper ore Of semiconductors. , 67. The method for manufacturing a polymer thin film as described in item 66 of the scope of patent application, 1245819, the scope of the application for patents among which: πHai semiconductor-nano crystal system is selected from the group consisting of CdSe, CdTe, InP, GaAs, CuInS2, CuInSe2, AlGaAs, InGaAs , Ge, and Si. 5 68. The method for manufacturing a polymer film according to item 51 of the patent application, wherein: the semiconductor and the nanocrystal are selected from the group consisting of CdSe and CdTe. Of thin film, 10 Among them: A part of the semiconductor-nano crystal is branched nano crystal. 70. The method for manufacturing a polymer film as described in item 69 of the scope of the patent application, wherein: a part of the scabbard-like nanocrystal has at least two arms, and the arms are not all the same length. 71. The method for manufacturing a polymer film according to item 69 of the scope of the patent application, wherein: the branched nanocrystals all have the same shape. 72. The method for manufacturing a polymer film as described in item 69 of the scope of the application for patent, wherein 0: the annihilated nanocrystal has four arms and has tetrahedral symmetry. Yes. The method for manufacturing a polymer film according to item 73 of the scope of patent application, wherein: the branched nanocrystalline system is CdSe or CdTe, and is embedded in an amount of about 90% by weight 1245819 and the scope of patent application. 74. The method for manufacturing a polymer film as described in claim 51 of the scope of patent application, wherein: the film has a thickness of about 100 nm to about 350 nm2. 5 75. The method for manufacturing a polymer film as described in item 74 of Shenqing Patent, wherein: the film has a thickness of about 200 nm. 76. The method for manufacturing a polymer film according to item 51 of the scope of patent application, wherein: 10 the binary solvent mixture contains at least one selected from the group consisting of pyridine, aeroform, toluene, xylene, hexane, water, and dioxin 2, digas toluene and alkylamine (wherein the alkyl group may be branched or unbranched, and the length is between 2 and 20 carbon atoms), a solvent of butanol, methanol and isopropanol. 77. Method 15 for manufacturing a polymer film as described in item 5 of the patent application scope, wherein: the concentration of the binary solvent mixture is between about 1 and about 15% by volume. The method for manufacturing a polymer film according to item 2, wherein: 20 The concentration of the binary solvent mixture is between about 4 and about 12% by volume. 79. The method for manufacturing a polymer film according to item 78 of the scope of patent application Where the concentration of the binary solvent mixture is about 8% by volume. 1245819 Pick up and apply for patent fg around 80. The method for manufacturing a polymer film as described in item 76 of the scope of patent application, wherein: the binary solvent mixture contains a σ specific bite in aerosol. 81. The method for manufacturing a polymer film as described in item 51 of the scope of patent application, wherein: the deposited film is about 60. 〇 to about 200 ° C heating 82. The method of manufacturing a polymer film as described in the 81st patent scope of the patent, wherein: 10 The deposited film is at about 80 ° C to about 130 ° C Temperature heating 83. The method for manufacturing a polymer film as described in item 82 of the scope of patent application, wherein: the deposited film is heated at a temperature of about 120 ° C. 15 84. A method of manufacturing a photoactive film, comprising: dispersing semiconductor-nano crystals in a semiconducting conjugated polymer to provide a polymer-nano crystal composite, and a film that deposits the composite, and so on, The nanocrystalline is buried in the polymer at more than 5% by weight, and at least a part of the semiconductor-nanocrystalline has an aspect ratio of greater than 2. 85. The method for manufacturing a photoactive film as described in item 84 of the scope of patent application, wherein: at least a part of the semiconductor-nano crystal 柃 heads L 丨 has a vertical length of 1245819 greater than about 5, the patent application is Aspect ratio. 86. The method for manufacturing a photoactive film according to item 84 of the scope of the patent application, wherein: at least a part of the semiconductor-nanocrystal has an aspect ratio of greater than about 10. 87_ The method for manufacturing a photoactive film according to item 84 of the scope of the patent application, wherein: at least a part of the semiconductor-nanocrystal has an aspect ratio between about 5 and about 50. 87. The method for manufacturing a photoactive film as described in the item of the scope of patent application, wherein: at least a part of the semiconductor-nano crystal has an aspect ratio between about 2 and about 10. 89. The method for manufacturing a photoactive film according to item 84 of the scope of the patent application, 15 wherein: the semiconductive conjugated polymer has about 5 to about 99% by weight of semiconductor-nanocrystals buried therein . 90. The method for manufacturing a photoactive film according to item 84 of the scope of the patent application, wherein: 20 the semiconductor conjugated polymer has approximately 20 to 95% by weight of semiconductor-nanometers embedded therein crystallization. • The method for manufacturing a photoactive film as described in the item of the declared patent scope, wherein: the semiconducting conjugated polymer has approximately 50 and 95% by weight of 1245819 buried semiconductor-nai Rice crystals. 92. The method for producing a photoactive film according to item 84 of the scope of the patent application, wherein: the semiconductive conjugated polymer has about 90% by weight of a semiconducting-nanocrystalline crystal buried therein. 93. The method for manufacturing a photoactive film according to item 84 of the scope of application for a patent, wherein: the semiconductive polymer is selected from the group consisting of trans-polyethylene, polytonol, polythiophene, polyaniline, poly (P-phenylene) and poly (p-phenylene-phenylene) 10, polyfluorene, polyaromatic amine, poly (phenylene-phenylene) and its soluble derivatives . 94. The method for manufacturing a photoactive film according to item 93 of the scope of patent application, wherein: the conjugated polymer is selected from (poly (2-methoxy5- (2, -ethylhexyloxy) 15 p-elongation A group consisting of phenyl vinylene (MEH-PPV) and poly (3-hexylthiophene) (P3HT). 95. The method for manufacturing a photoactive film according to item 84 of the scope of patent application, wherein: Nanocrystals include rods having a length greater than about 20 nm. 2096. The method of manufacturing a photoactive film as described in item 84 of the patent application scope, wherein: the semiconductor-nanocrystals include A rod with a length of about 200 nm. 97. The method for manufacturing a photoactive film as described in item 96 of the scope of patent application, 1245819, and the scope of patent application where: The semiconductor-nanocrystal includes Time length 98.  According to the method for manufacturing a photoactive film described in item 84 of the scope of patent application, 5 wherein: the semiconductor-nanocrystal contains a rod of about 7 nm X 60 nm. 99.  The method for manufacturing a photoactive thin film as described in item 84 of the scope of the patent application, wherein = the semiconductor-neo crystal includes a semiconductor selected from group II-VI, group III-V, group IV 10 and a third-grade mica copper mine The semiconductors that make up the group. 100.  The method for manufacturing a photoactive film according to item 99 of the scope of patent application, wherein: the semiconductor-nano crystal system is selected from the group consisting of CdSe, CdTe, InP, GaAs, CuInS2, CuInSe2, AlGaAs, InGaAs, Ge, and Si 15 groups. 101.  The method for manufacturing a photoactive film according to item 84 of the patent application scope, wherein: the semiconductor-nano crystal system is selected from the group consisting of CdSe and CdTe 〇 20 102. The method for manufacturing a photoactive film according to item 84 of the patent application scope, wherein: a part of the semiconductor · nanocrystal is a branched nanocrystal. 103. The method for manufacturing a photoactive film as described in item 102 of the scope of patent application, wherein: 1245819, the scope of the patent application The part of the knife-shaped nanocrystal has at least two arms, and the arms have the same length. 104. The method for manufacturing a photoactive film as described in item 1G2 of the Chinese Patent Application ′, wherein all of the 5 δHai branched nanocrystals have the same shape. 105. The method for manufacturing a photoactive film according to item 102 of the scope of patent application, wherein: ^ the branched nanocrystal has four arms and has tetrahedral symmetry. 106.  The photoactive thin film 10 as described in item 105 of the application patent scope, wherein: 'The branched nanocrystalline is CdSe or CdTe, and is embedded in an amount of about 90% by weight. 107.  The method for manufacturing a photoactive film according to item 84 of the patent application scope, wherein: * 15 The film has a thickness of about 100 nm to about 350 nm. 108.  The method for manufacturing a photoactive film as described in the scope of patent application No. 107, wherein: the film has a thickness of about 200 nm. 109. The method 20 for manufacturing a photoactive film according to item 84 of the Shen Qing patent scope, wherein: the semiconductor-nano crystal and the semiconducting polymer are co-dissolved in a binary solvent mixture, and the binary solvent The mixture contains at least one selected from the group consisting of pyridine, chloroform, toluene, xylene, hexane, water, dichlorobenzene, THF, dichloromethane, fired 1245819, and patented patented amines (wherein the alkyl chain may be branched Or unbranched, with a length between 2 and 20 carbon atoms), butanol, methanol and isopropanol. no. The method for manufacturing a photoactive film according to item 109 of the patent application, wherein the concentration of the 27L solvent mixture is between about i and about 15% by volume. A method for an active film, wherein: The concentration of the two 70 solvent mixture is between about 4 and about 12% by volume. 112. The method for manufacturing a photoactive film according to item 111 of the patent application scope, wherein: the binary solvent The concentration of the mixture is about 8 vol. 113. The method for manufacturing a photoactive film according to item 109 of the scope of patent application, wherein: the one-component solvent mixture contains σ-pyridine in aerosol. 114. The method for manufacturing a photoactive film according to item 84 of the patent application scope, wherein: the film to be deposited is about 60 ° C to about 200 ° C. (: Heating at temperature 011 5) The method for manufacturing a photoactive film as described in item 1 of the scope of the patent application, wherein: the deposited film is heated at a temperature of about 8 (TC to about 130 ° C) 1245819, Patent application range 116 · The method for manufacturing a photoactive film as described in item 84 of the patent application range, wherein: the deposited film is heated at a temperature of about 120 ° C. 117 · —a photovoltaic device, including: 5 a conjugated conductive polymer layer having semiconductor-nano crystals dispersed therein, and the device having  1.5 The power conversion efficiency is greater than 1% at full illumination, wherein at least a part of the semiconductor-nanocrystal has an aspect ratio greater than 10 to about 2. 11 8 · The photovoltaic device according to item 117 of the scope of patent application, wherein: the device has a power conversion efficiency of greater than 5%, of which 15 at least a part of the semiconductor-nano crystal has an aspect ratio greater than about 2 ratio. 119. The photovoltaic device according to item No. Π8 of the patent application scope, wherein: the device has a power conversion efficiency of greater than 10%. 2〇 120. The photovoltaic device according to item 117 of the patent application scope, wherein: the device has a power between about 1% and about 30%. Conversion efficiency. 121. The photovoltaic device as described in item 120 of the scope of Shen 5 Qing patent, in which: 1245819, patent application scope This device has a power conversion efficiency between about 2% and about 30%. The photovoltaic device according to item 121 of the patent application scope of the application, wherein: ′, the device has a power conversion efficiency between about 5% and about 15%. 5 123. The photovoltaic device according to item 7 of the scope of the patent application, wherein: ′, The Pei Zhi has about 1. 7% power conversion efficiency. 124. The photovoltaic device according to item 7 of the scope of the patent application, wherein: ′, 10 At least a part of the semiconductor-nanocrystal has an aspect ratio greater than about 5. 125. The photovoltaic device according to item 17 of the patent application, wherein: at least a part of the semiconductor-nanocrystal has an aspect ratio greater than about 10. 15 丨 26. The photovoltaic device according to item 117 of the scope of patent application, wherein: 至少 At least a part of the semiconductor nanocrystal has an aspect ratio between about 5 and about 50. 127. The photovoltaic device according to item 117 of the scope of patent application, wherein: at least a part of the 11H semiconductor-nano crystal has an aspect ratio of about 2 to about 20. 128. The photovoltaic device according to item 117 of the patent application scope, wherein: the semiconductive conjugated polymer has about 5 and about 99% by weight of semiconductor-nanocrystals buried therein. 129. The photovoltaic device according to item 117 of the scope of patent application, wherein: 1245819 The scope of the patent application The semi-co-light polymer has approximately 20% and 95% by weight of semiconductor-naphthalene buried therein. Rice crystals. 130. The photovoltaic device according to item 117 of the scope of patent application, wherein: the semiconducting conjugated polymer has approximately 50 and 95% by weight of semiconductor-nano crystals buried therein. 131. The photovoltaic device according to item 117 of the scope of patent application, wherein: the semiconducting conjugated polymer has approximately 90% by weight of a semiconductor buried therein. Nanocrystals. 132. The photovoltaic device according to item 117 of the patent application scope, wherein: 10 the semiconductive conjugated polymer is selected from the group consisting of trans-polyacetylene, polypyrrole, polythiophene, polyaniline, poly (p-phenylene) Groups) and poly (p-phenylene-phenylene), polyfluorene, polyaromatic amines, poly (phenylene-phenylene) and its soluble derivatives. 133. The photovoltaic device according to item 132 of the scope of patent application, wherein: 15 the conjugated polymer is selected from (poly (2-fluorenyloxy 5- (2, -ethylhexyloxy)) A group consisting of benzylic vinyl) (MEH-PPV) and poly (3-hexylmethylphene) (P3HT). 134. The photovoltaic device according to item 117 of the scope of patent application, wherein: the semiconductor-nai The rice crystal includes a rod having a length greater than about 20 nm. 20 135. The photovoltaic device according to item 117 of the scope of patent application, wherein: the semiconductor-nano crystal contains a crystal having a length between about 20 nm and about 200 nm. 136. The photovoltaic device according to item 135 of the scope of patent application, wherein: the semiconductor-nano crystal includes a rod having a length of 1245819 between about 60 nm and about 110 nm, and a scope of patent application. 137 · The photovoltaic device according to item 117 of the patent application scope, wherein: the semiconductor-nano crystal contains a rod of about 7 nm x 60 nm. The photovoltaic device according to item 117 of the patent application scope, wherein: 5 The semiconductor-nano crystal contains a group selected from group II-VI, group mv, 1 ¥ Group of semiconductors and semiconductors of the group consisting of tertiary mica copper ore. 139. The photovoltaic device according to item 138 of the patent application scope, wherein: the semiconductor-nano crystal system is selected from the group consisting of CdSe, CdTe, lnp, GaAs, CuInS2, CuInSe2, AlGaAs, InGaAs, Ge, and Si10 group. 140. The photovoltaic device according to item 117 of the scope of patent application, wherein the semiconductor-nano crystal system is selected from the group consisting of CdSe & CdTe. 141. The photovoltaic device according to item 117 of the patent application scope, wherein: 15 A part of the semiconductor-nano crystal is a branched nano crystal. 142. The photovoltaic device as described in item 141 of the Shin-Ken patent scope, wherein a part of the branched nanocrystal has at least two arms, and the arms are not all the same length. 143. The photovoltaic device described in item 141 of the Shenjing patent scope, wherein the branched nanocrystals of 5 ° H all have the same shape. 144. The photovoltaic device according to item 141 of the scope of patent application, wherein: the 5 nm branched nanocrystal has 4 arms and has tetrahedral symmetry. 145. The photovoltaic device according to item 144 of the scope of patent application, wherein: the branched nanocrystalline system is CdSe or CdTe, and is embedded in an amount of about 90% by weight of 1245819 and the scope of patent application. 146.  The photovoltaic device according to item 117 of the application, wherein: the film has a thickness of about 100 nm to about 350 nm. 147.  The photovoltaic device according to item 146 of the scope of patent application, wherein: 5 the film has a thickness of about 200 nm. 148 · A photovoltaic device, comprising: a first planar electrode, a thin film comprising a semiconducting conjugated polymer having a semiconductor-nano crystal buried therein, the thin film being deposited on the first plane On the electrode 10, and a second electrode, which is opposite to the first electrode, and an electron hole injection layer, which is placed between the thin film polymer layer and the first planar electrode, wherein the semiconductor_nanometer At least a portion of the crystals have an aspect ratio of greater than 15 to about 2. 149.  The photovoltaic device according to item 148 of the patent application scope, wherein: the electron hole injection layer comprises PEDOT: PSS. 150.  The photovoltaic device according to item 149 of the patent application scope, wherein 20: the first electrode includes ITO and the second electrode includes A1. 151. The photovoltaic device according to item 148 of the scope of patent application, wherein at least a part of the Λ half 'body-nano crystal has an aspect ratio greater than about 5. 1245819 Patent application scope 152. The photovoltaic device according to item 148 of the patent application scope, wherein: at least a part of the semiconductor-nano crystal has an aspect ratio greater than about 10. 153. The photovoltaic device according to item 148 of the scope of patent application, wherein: at least a part of the 5 ° semiconductor semiconductor nanocrystal has an aspect ratio between about 5 and about 50. 154. The photovoltaic device according to item 148 of the patent application scope, wherein: at least a part of the semiconductor-nano crystal has an aspect ratio between about 2 and about 〇. 10 155. The photovoltaic device according to item 148 of the scope of patent application, wherein: the semiconductive conjugated polymer has about 5 to about 99% by weight of semiconductor-nanocrystals buried therein. 156. The photovoltaic device according to item 148 of the scope of patent application, wherein: the semiconducting conjugated polymer has approximately 20 and 95% by weight of semiconductor-nano crystals buried therein. 157. The photovoltaic device according to item 148 of the scope of patent application, wherein: the semiconductive conjugated polymer has about 50 to 95% by weight of semiconductor-nanocrystals buried therein. 158. The photovoltaic device according to item 148 of the scope of patent application, wherein: 20 the semiconductive conjugated polymer has approximately 90% by weight of semiconductor-nanocrystals buried therein. 159. The photovoltaic device according to item 148 of the scope of patent application, wherein: the semiconducting conjugated polymer is selected from the group consisting of trans-polyacetylene, polypyrrole, polythiophene, polyaniline, and poly (para-elongation) Phenyl) and poly (p-phenylene_vinyl) 1245819, patent application scope, polyfluorene, polyaromatic amine, poly (thienyl-vinyl) and its soluble derivatives Ethnic group. 160.  The photovoltaic device according to item 159 of the application, wherein: the conjugated polymer is selected from (poly (2-methoxy5- (2'-ethylhexyloxy) 5 A group consisting of vinyl) (MEH-PPV) and poly (3-hexylthiophene) (P3HT). 161.  The photovoltaic device according to item 148 of the patent application scope, wherein: the semiconductor-nanocrystal includes a rod having a length greater than about 50 nm. 162.  The photovoltaic device according to item 148 of the scope of patent application, wherein: 10 the semiconductor-nanocrystal comprises a rod having a length between about 20 nm and about 200 nm. 163.  The photovoltaic device according to item 162 of the patent application scope, wherein: the semiconductor-nano crystal includes a rod having a length between about 60 nm and about 110 nm. 15 164. The photovoltaic device according to item 148 of the patent application scope, wherein: the semiconductor-nano crystal includes a rod of about 7 nm X 60 nm. 165. The photovoltaic device according to item 148 of the patent application scope, wherein: the semiconductor-nano crystal includes a group selected from the group consisting of II-VI, III-V, IV semiconductors, and tertiary mica copper ore Of semiconductors. 20 166. The photovoltaic device according to item 165 of the application, wherein: the semiconductor-nano crystal system is selected from the group consisting of CdSe, CdTe, InP, GaAs, CuInS2, CuInSe2, AlGaAs, InGaAs, Ge, and Si. 167. The photovoltaic device according to item 148 of the patent application scope, wherein: 1245819, patent application scope ° Xuan semiconductor-nano crystal system is selected from the group consisting of CdSe and CdTe. The photovoltaic device according to the item, wherein: part of the semiconductor-nanocrystal is a branched nanocrystal. 5 169. The photovoltaic device according to item 168 of the Shen Jing patent scope, wherein: a part of the 5 nm branched nanocrystal has at least two arms, and the arms are not all the same length. Π0. The photovoltaic device according to item 169 of the patent application scope, wherein: the branched nanocrystals all have the same shape. 10 171. The photovoltaic device according to item 169 of the patent application, wherein: the branched nanocrystal has four arms and has tetrahedral symmetry. 172. The photovoltaic device according to item 171 of the scope of patent application, wherein: the branched nanocrystalline system is CdSe or CdTe, and is embedded in an amount of about 90% by weight. 15 173. The photovoltaic device according to item 148 of the scope of patent application, wherein: the film has a thickness of about 100 nm to about 350 nm. 174.  The photovoltaic device according to item 173 of the patent application scope, wherein: the film has a thickness of about 2000 nm. 175.  A thin film comprising: 20 polymer 'having a nano junction buried therein, wherein at least a portion of the semiconductor-nano crystal has an aspect ratio crystal greater than about 2. 176. A method for making a thin film, including one or more of the following steps: (a) washing the nanocrystals at least once with a solvent; 1245819, applying for patent scope (b) making the cleaned nanostructured mixture; The crystals and polymers are dissolved in a solvent to produce the mixture (C), wherein the semiconductor-nanocrystal has at least one eighteenth of four parts having an aspect ratio greater than about two. 177. A photovoltaic device, comprising: a polymer layer having nanometers dispersed therein, wherein at least a portion of the semiconductor-nanocrystal has an aspect ratio greater than about 2. 10 178. A photovoltaic device, comprising: a first electrode, a thin film including a polymer on the first electrode, and a second electrode, wherein at least a portion of the semiconductor-nanocrystal has a diameter greater than about 15 Aspect ratio of 2.