DE102011077706A1 - Bicontinuous, interpenetrating composite useful in photovoltaic device e.g. solar cell, comprises semiconducting organic phase, semiconducting particulate phase, p-n junctions at interfaces, and processing aid - Google Patents

Abstract

Compositions and articles comprising and methods of making a bi-continuous interpenetrating composite of a semiconducting organic phase, a semiconducting particulate phase and a plurality of p-n junctions at interfaces between the semiconducting organic phase and the semiconducting particulate phase. The bicontinous interpenetrating composite is a new photovoltaic material that can increase photovoltaic conversion efficiency and reduce the cost of manufacturing photovoltaic devices.

Description

AREA OF REVELATION

The invention relates to photoactive materials in photovoltaic devices, in particular solar cells.

BRIEF DESCRIPTION OF THE RELATED TECHNIQUE

In 1 Elements of a photovoltaic device (solar cell) are shown. The goal is to generate power by: (1) generating a strong short circuit current I _sc , (2) generating a high open circuit voltage V _oc , and (3) minimizing parasitic current loss mechanisms. I _sc depends on: 1) the generation of radiation-generated carriers and 2) the collection of light-generated carriers. The absorption of incident photons to produce electron-hole pairs as in 2 where negative and positive circles represent electron (negative carrier) or hole (positive carrier) occurs when the incident photon has an energy (E _ph ) greater than the band gap (E _g ). Photons with E _ph <E _g are not absorbed and are lost. If a photon has energy above E _g , the excess energy above E _g is lost as heat. The value of the band gap thus determines the maximum possible current and the heat generated. If the photon absorber is a single bandgap material, available photons are lost and the cell operates at a reduced efficiency.

Current photovoltaic devices use radiation collection materials in planar film architectures. Radiation incident on a planar surface will have a reflected component that reduces absorption efficiency - often anti-reflective coatings on material interfaces are used to reduce reflective losses, but reflective losses can not be eliminated. The use of the stacked film architecture (disclosed in US patent application Ser. No. 280264475A1) or series stacked but electrically isolated solar cells (disclosed in US Pat U.S. Patent 4,094,704 ) moderately reduces absorption and does not eliminate reflective losses. In addition, the integration of anti-reflective coatings and multi-layer device architectures adds complexity and cost to the array.

The use of organic-inorganic composites in photovoltaic devices is known. The Japanese Patent Application 24071682A2 discloses a composite material (titanium oxide mixed with a conductive polymer) that is used to create a diode that is external to the solar cell and used to control the power line. The U.S. Patent 4,971,633 discloses a thin film of porous Al ₂ O ₃ styrene acrylate composite used as a thermally conductive dielectric layer that electrically insulates the solar cells and the heat sink. The Japanese Patent Application 221 00793A2 discloses a composite material used to form a solar battery. The U.S. Patent 6,261,469 discloses three-dimensional periodic arrays of spherical particles processed through one or more extraction and infiltration steps to produce an organic-inorganic composite. The U.S. Patent 6,710,366 discloses a nanocomposite material containing a matrix material and a plurality of quantum dots scattered in the matrix material having a nonlinear refractive index and increased radiation absorption between 3 × 10 ^-5 cm and 2 × 10 ^-4 cm. US Patent Application 290071539A1 discloses a nanocomposite containing amorphous silicon and nanocrystalline silicon, thereby improving the degree of conversion of a solar cell.

The U.S. Patent 7,341,774 discloses an electronic or optoelectronic device having a interpenetrating network of nanostructured film material having a high surface area to volume ratio and an organic-inorganic material, thereby forming a nanocomposite. This material is formed by depositing the high surface area to volume ratio material onto an electrode substrate and forming the interpenetrating network by inserting the organic-inorganic network into the void volume of the high surface area to volume ratio material, while at the electrode is appropriate. The organic-inorganic nanocomposite material serves as the filler surrounding the basic elements of the film.

Konarka (2008 Nanotechnology Symposium, Nov. 20, 2008, Evanston, IL) disclosed composites of poly-3-hexylthiophene / phenyl-C61-butyric acid methyl ester (P3HT-PCBM) as light harvesting materials in photovoltaic systems. Solar conversion efficiencies of 5% -6.5% were claimed, indicating scattered composites rather than bicontinuous interpenetrating morphologies.

SUMMARY OF THE INVENTION

One embodiment of the disclosure is a bicontinuous interpenetrating composite comprising a semiconductive organic phase, a semiconducting particulate phase, and a plurality of pn junctions at interfaces between the semiconducting organic phase and the semiconducting particle phase, wherein the semiconductive organic phase and the semiconductive particle phase interpenetrate and are bicontinuous.

Another embodiment is a photovoltaic device that includes a conductive front contact, a conductive rear contact, and the bicontinuous interpenetrating composite between the front contact and the rear contact.

Yet another embodiment is a method of making the bicontinuous interpenetrating composite comprising admixing an organic polymer, a first plurality of particles, and a second plurality of particles, wherein the first plurality of particles has a surface treatment greater than the second plurality of particles is.

BRIEF DESCRIPTION OF THE DRAWING FIGURES

1 is an exemplary illustration of the elements of a solar cell.

2 is an example of the absorption of incident photons to produce electron-hole pairs.

3 shows a solar cell.

DETAILED DESCRIPTION OF THE INVENTION

The present invention utilizes an organic particulate composite having a bicontinuous interpenetrating morphology (i.e., a bicontinuous interpenetrating composite). The composite acts as the radiation collection element in a photovoltaic device. The bicontinuous interpenetrating composite contains two main bulk phases: an organic phase and a particle phase. In one embodiment, both phases can absorb incident radiation and generate radiation generated carriers. The bicontinuous interpenetrating composite further includes a p-n junction at the interface between the two phases, which prevents recombination of radiation-generated carriers and allows the collection of radiation-generated carriers. In one embodiment, the presence of the electric field at the p-n junction interface spatially separates electrons and positive carriers.

In one embodiment, the bicontinuous interpenetrating composite consists essentially of a three-dimensional bulk material containing the two phases, organic phase and the particle phase. In this embodiment, the organic phase is a semiconducting polymer of either n-type or p-type. The particulate phase is a compound of particles or composite particles containing semiconductor and / or metal materials having complementary electrical properties to the organic phase (ie, when the organic phase is an n-type semiconducting polymer, the particulate phase is a p-type material alternatively, the n-type particle phase is when the organic phase is p-type). One method of making the bicontinuous interpenetrating composite is by surface treatment of the particles of the particle phase and admixing of the organic polymer and the surface-treated particles to form the bicontinuous interpenetrating morphology.

In one embodiment, the particle phase is a continuous or semi-continuous network of particles containing an inorganic semiconductor and / or metal material. Examples include particles of semiconducting polymers (described in more detail below), inorganic materials, semiconductor materials and metal materials. Examples of inorganic materials include alumina, zirconia, silica and mixtures thereof. Examples of inorganic semiconductors include silicon, germanium and mixtures thereof, titanium dioxide, zinc oxide, indium tin oxide, antimony tin oxide and mixtures thereof, 2-6 semiconductors containing compounds of at least one divalent metal (zinc, cadmium, mercury and lead) and at least one divalent nonmetal (Oxygen, sulfur, selenium and tellurium), such as zinc oxide, cadmium selenide, cadmium sulfide, mercury selenide and mixtures thereof, 3-5 semiconductors, are the compounds of at least one trivalent metal (aluminum, gallium, indium and thallium) with at least one trivalent one Non-metals (nitrogen, phosphorus, arsenic, antimony) are, such as. Gallium arsenide, indium phosphide and mixtures thereof, and Group 4 semiconductors, including hydrogen-terminated silicon, germanium and alpha-tin, and combinations thereof.

Examples of metal materials include gold, silver, platinum particles and mixtures thereof, metal clusters such as nickel, palladium, gold, copper and mixtures thereof and suboxidized metal oxides such as Ti-rich titanium oxide, Zn-rich zinc oxide, Zr-rich zirconia and mixtures thereof.

Types of particulate semiconductor materials result from variants that include (1) single or mixed elemental compounds including alloys, core / shell structures, doped particles and combinations thereof, (2) single or mixed shapes and sizes, and combinations thereof, and (3) a single form of crystallinity or a portion or mixture of crystallinity and combinations thereof.

Preferably, the particle phase contains a plurality of particles with different band gaps. The band gap of semiconductors can be modified by including small amounts of an element replacing one of the existing elements in the structure without changing the crystal structure. Examples include replacing a small amount of aluminum in alumina with indium or small amounts of oxygen with nitrogen or sulfur in titanium oxides. Also, compounds of two semiconductors having similar structures can be used to change the band gap, such as compounds of zinc sulfide and cadmium selenide or alumina and indium oxide. Another way of modifying the bandgap is to coat the semiconductor with another material, such as a metal, for example, aluminum, copper, silver, or gold; the band of the semiconductor and the metal moves at the interface with each other, thereby affecting the band gaps at the interface. Another way of modifying the bandgap is by mixing doped and undoped Group 4 semiconductor particles. For example, p-type dopants for silicon include boron, aluminum, and gallium, and n-type dopants for silicon include phosphorus, arsenic, and antimony.

Examples of particles that can be used as the particle phase include semiconductor nanocrystals. Semiconductor nanocrystals have been known for many years, and the production of this material is known, for example, in US Pat CB Murray, CR Kagan and MG Bawendi, Annu. Rev. Mater. Sci., 2000, 30, 545 ; CB Murray, DJ Norris and MG Bawendi, J. Am. Chem. Soc., 1993, 115, 8706 ; and JE Bowen Katari, VL Colvin and AP Alivisatos, J. Phys. Chem., 1994, 98, 4109 described. A particular feature of semiconductor nanocrystals is that their bandgap can be controlled by their size. Semiconductor nanocrystals can be formed as mixtures with a core-shell structure; a first composition forms the core (for example, CdSe), and this core is surrounded by a shell of a second composition (for example, ZnS). The production of these materials is in MA Hines and P. Guyot-Sionnest, J. Phys. Chem., 1996, 100, 468 , described. Examples include the core / shell pairs CdSe / ZnS, CdSe / CdS, InAs / CdSe, InAs / InP, ZnS / CdSe, CdS / CdSe, CdSe / InAs and InP / As.

Semiconductor nanocrystals can be formed with capping groups on their surfaces. Capping groups are parts attached to the surface of the semiconductor nanocrystals and are taken up during the synthesis of colloidal nanocrystals. In the form of colloids they are easily manipulated and can be mixed with a solvent, including non-polar and polar organic solvents such as alkanes (for example hexane and pentane), ethers (diethyl ether and tetrahydrofuran), benzene, toluene, styrene, dichloromethane, styrene, Xylene, dimethylformamide, carbonates (propylene carbonate), dimethyl sulfoxide and mixtures thereof. The capping groups are readily interchangeable, as in Bruchez Jr., M., Moronne, M., Gin, P., Weiss, S. & Alivisatos, AP Science, 1998, 281, 2013-2016 ; and Chan, WCW & Nie, S. Science, 1998, 281, 2016-2018 is described.

The particle phase preferably contains a plurality of particles of 1 nm to 5 micrometers in diameter. For example, the particle diameter may be from 1 nm to 500 nm, or the particle diameter may be from 1 nm to 100 nm. If the plurality of particles in the particle phase has a diameter of less than 100 nm and the radiation collection composite is thin, the internal shadowing may be substantially zero, whereby the efficiency may be increased.

There is self-assembly or self-assembly of the particles into a linked bulk phase. The production of the particulate phase using self-assembly is based on the selection of a degree of surface treatment for the particles which attract and repel each other and the organic phase. An "attractive" or "repulsive" force is intended to mean a surface force that isolates the two phases into a bicontinuous interpenetrating morphology. The self-assembly of the particles is controlled by dispersion forces quantified by the Hamaker constant, the description of the Hamaker constant being as in U.S. Pat U.S. Patent 7,387,851 is fully incorporated herein by reference. The untreated portion of the surface of the particles will attract each other, and the treated portion of the surface of the particles will be attracted to the organic phase resulting in a controlled accumulation of the inorganic particles and a continuous or semi-continuous network of particles.

In another embodiment, the particles may be made more compatible with the organic phase by surface treatment. Examples of surface treatment agents include phenylene agents, for example, triphenylethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, triphenyltin hydride, triphenyltin hydroxide, tetraphenyltin, hexaphenylditin, and mixtures thereof. These surface treatment agents may facilitate the formation of a pn junction and, structurally, the pn junction comprises the reaction product of the surface treatment agent and the plurality of particles of the particle phase. For example, the pn junction may comprise a phenylene located opposite the particle phase (ie, the reaction product of the phenylene agent with the plurality of particles of the particle phase or other phenylene agents for effective encapsulation of particles of the particle phase). The surface treatment agent can separate the organic phase and the particle phase at least by molecular dimensions (about 0.1 nm to 20 nm). Preferably, the surface treatment blocks hole (cation) transport, and preferably, the surface treatment introduces an electron-rich material, such as a material with electrons that are Π-conjugated, to the surface of the particles.

The amount of surface treatment of the particles, that is, the average percentage of surface treatment versus a plurality of particles, can range from about 20% to about 80%. The amount of surface treatment of the particles may be 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75% or 80% of the surface. For at least part of the particles, only part of their surfaces are treated. Preferably, at least a portion of the particles have untreated surfaces. By forming a mixture of particles of varying degrees of surface treatment, a continuous phase will self-organize. Preferably, a first plurality of particles has an amount of surface treatment that is greater than a second plurality of particles. For example, the first plurality of particles may have a surface finish of 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, or 80%, and the second plurality may have a surface finish of 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70% or 75%. Preferably, the first plurality of particles has an amount of surface treatment that is 20%, 25%, 30%, 35%, 40%, 45%, or 50% higher than the second plurality of particles.

In one embodiment, the bicontinuous interpenetrating composite is prepared by forming a mixture of liquid monomer, a solvent, and colloidal semiconductor nanocrystals, followed by polymerization of the monomer.

The organic phase contains organic semiconductors, differently labeled Π-conjugated polymers, conducting polymers, or synthetic metals that are inherently semiconductive due to Π-conjugation between carbon atoms along the polymer back wheel. Its structure contains a one-dimensional organic backbone that allows electrical conduction following n- or p-doping.

Well studied classes of organically conductive polymers include poly (acetylene) s, poly (pyrrole) s, poly (thiophene) s, polyanilines, polythiophenes, poly (p-phenylsulfide), poly (para-phenylvinylene) s, (PPV), and PPV Derivatives, poly (3-alkylthiophene), polyindole, polypyrene, polycarbazole, polyazulen, polyazepine, poly (fluoride) s and polynaphthalene. Other examples include polyaniline, polyaniline derivatives, polythiophene, polythiophene derivatives, polypyrrole, polypyrrole derivatives, polythaphenylene derivatives, polythiophene derivatives, polyparaphenylene, polyparaphenylene derivatives, polyacetylene, polyacetylene derivatives, polydiacethylene, polydiacethylene derivatives, polyparaphenylenevinylene, polyparaphenylenevinylene derivatives, polynaphthalenes and polynaphthalene derivatives, polyisothianaphthene, polyheteroarylenevinylene wherein the heteroarylene group is e.g. Thiophene, furan or pyrrole, polyphenylene sulfide, polyperinaphthalene, polyphthalocyanine etc. and their derivatives, copolymers thereof and mixtures thereof. As used herein, the term derivatives means that the polymer is prepared from side chain or group substituted monomers.

The method for polymerizing the conductive polymers may include electrolytic oxidation polymerization, chemical oxidation polymerization, and catalytic polymerization. The polymer obtained by the polymerization of the liquid monomer may be neutral and / or non-conductive until doped. Therefore, a neutral and / or nonconductive polymer is subjected to p-type doping or n-type doping to form the conductive polymer. In another embodiment, the semiconductor polymer may be doped chemically or electrochemically. The dopants are not particularly limited; Preferably, the dopant does not adversely affect the photochemical and / or chemical stability of the particle formations. Examples include a substance having the ability to accept an electron pair, such as a Lewis acid. Dopants may include, for example, hydrochloric acid, sulfuric acid, organic sulfuric acid derivatives such as parafichloric acid, polystyrene sulfuric acid, alkylbenzenesulfuric acid, camphor sulfuric acid, alkyl sulfuric acid, Sulfosalicylic acid, other sulfuric acids, iron chloride, copper chloride, iron sulfate or mixtures thereof.

The organic particulate composite can be processed as a liquid, thereby increasing the production rate and reducing the manufacturing cost. The light harvesting material can be processed using known solution processing techniques, such as spray, curtain coating, ink jet, and other similar processes using conventional film processing equipment.

The composite is preferably formed by first forming a liquid which dissolves the particle phase and the polymer in solution or contains monomers of the polymer dissolved in solution. Any solvent may be used in which the polymer or its monomers dissolve and the particles are scattered. Examples of solvents include water, alcohols such as methanol, ethanol, propanol, butanols, glycerine, acetonitrile, tetrahydrofuran, dimethylformamide, N-methylformamide, glycols such as ethylene glycol, propylene glycol, carbonates such as propylene carbonate, dimethyl sulfoxide and mixtures thereof. When the polymer is formed by polymerization of monomers or prepolymers by default, any solvent can be used in which the remaining components can be dissolved or scattered. Examples include the above-mentioned solvents as well as organic solvents. When the polymer is standardly formed from monomers, the monomer itself may be used in place of the solvent or with a small amount of solvent to control viscosity as long as the remaining components can be dissolved or scattered.

Process aids can also be used. Examples of processing aids include activated carbon, colloidal metals such as colloidal gold, surface treatment agents and graphene. These conductive materials will naturally migrate to the interfaces and help prevent the formation of defects or structures that could trap electrons and / or holes, allowing the continuous networks to conduct away the electrons and holes as they form.

In another embodiment, the bicontinuous interpenetrating composite is an active layer in a photovoltaic device. The photovoltaic device includes a conductive front contact and a conductive rear contact with the bicontinuous interpenetrating composite disposed therebetween. To facilitate the migration of photoelectric charges in the bicontinuous interpenetrating composite, the bicontinuous interpenetrating composite may be sandwiched between an n-type layer and a p-type layer, with either the conductive front or back contact forming the layer of the n-type contacted and the other conductive contact contacted the p-type layer.

1 and 3 show a photovoltaic device. As shown, a photovoltaic device 16 an optional transparent plastic base 2 , a layer of the particles on the basis preferably without surface treatment 4 on the layer of particles an absorber layer containing the bicontinuous interpenetrating composite 6 comprises and on the composite a layer of the organic phase 8th include. When exposed to light, the composite may form radiation-generated carriers that are separated and conducted separately through either the organic phase or the particle phase to the organic phase layer. The charge carriers then travel via conductive contacts (a front contact) 10 , (a back contact) 12 to a device 14 , The device can measure current or voltage or can store or use the electricity to do useful work. Preferably, when doped, the particles have complementary electrical properties of the organic phase. Optionally, other elements typically found in a photovoltaic device may be included.

The present invention can increase photovoltaic efficiency through several mechanisms. Incident radiation can be absorbed by both phases of the composite, with the particle phase containing a number of chemical properties and particle sizes. Each component of the composite may have a specific band gap, but the assembled composite has a distribution of band gaps that can be tailored to fully absorb or nearly fully absorb all incident radiation. In practice, a monolayer solar cell with triple junction (or higher) can be made. Net photoelectric conversion efficiencies can be significantly greater than conventional multiple-junction planar devices; however, photoelectric conversion efficiencies of CIGS or CdTe are about 10% to 12%. In one embodiment, the present invention photoelectric conversion efficiencies of 15% to 40%, 20% to 40% or 25% to 35%.

The use of zinc oxide as at least one component of the particle phase can increase the absorption of UV radiation. Not only can the radiation absorption spectrum be shifted to higher frequencies, but by absorbing UVA radiation in the particle phase, potential damage to the organic phase can be reduced and the device lifetime can be higher than corresponding devices containing organic light absorbing materials.

The interface in the composite material can have a large ratio of three-dimensional surface area to volume and act as an internal scattering element. Incident radiation can be scattered by forward reflection from the organic-particulate interfaces in the composite material therein - effectively increasing the path length of the material and possibly providing a larger effective radiation absorption area.

The bicontinuous interpenetrating morphology can provide three-dimensional connectivity - mechanically and electrically. Electrons can flow from one phase and positive charge carriers can flow from the other phase. The three-dimensional connectivity can enable electrical connections to device edges and can prevent shading effects caused by surface electrodes that reduce the efficiency of current devices.

The interface in the composite material has a large ratio of three-dimensional surface area to volume and can act as a p-n junction. The spatial distance between two interfaces within the bicontinuous interpenetrating material is small, on the order of 1 nm to 1 micrometer, and minority carriers will have short diffusion paths to the interface, possibly reducing the likelihood of electron-hole recombination events, and possibly Photovoltaic efficiency is increased.

EXAMPLES

example 1

A composite formed using semiconductive p-type polymer: A p-type organic semiconductor, poly (3,4-ethylenedioxythiophene) (PEDOT) is dissolved in a suitable solvent.

60 nm diameter particles of antimony tin oxide (ATO) are surface treated with phenyltriethoxysilane (PTES) to produce two types of material. The first is 30% surface treated (ATO-PTES-30) and the second is 60% surface treated (ATO-PTES-60). Two similar types of tin oxide (TO) are manufactured: TO-PTES-30 and TO-PTES-60.

PEDOT is mixed with particle phase to form 4 mixtures. The PEDOT blends were coated on a plastic substrate using solvent-based doctor blading technique (drip, spin-on, inkjet, screen, spray, and other solvent-based coating techniques would be equally acceptable).

Bicontinuous interpenetrating morphologies were formed while ratios of PEDOT / total particles varied between 40% and 60%. The ratio of the -60 / -40 particle ratio is 1, but this ratio can be varied to give specific device properties. The ratio ATO / TO is controlled so as to give the desired electrical phase conductivity.

Example 2

A composite formed using semiconducting n-type polymer: An n-type organic semiconductor, poly (pyridine-2,5-diyl) (PPD), is dissolved in a suitable solvent.

60 nm diameter alumina (AO) particles are surface treated with phenyltriethoxysilane (PTES) to produce two types of material. The first is 30% surface treated (AO-PTES-30) and the second is 60% surface-treated (AO-PTES-60).

PPD is mixed with particle phase to form 2 mixtures. The PPD blends were coated on a plastic substrate using the solvent-based Doctor Blading technique (drip, spin coat, ink jet, screen, spray, and other solvent based coating techniques would be equally acceptable).

Bicontinuous interpenetrating morphologies were formed while ratios of PPD / total particles varied between 40% and 60%. The ratio of the -60 / -40 particle ratio is 1, this ratio can but varied to give specific device characteristics.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• US 4094704 [0003]
• JP 24071682 A2 [0004]
• US 4971633 [0004]
• JP 22100793 A2 [0004]
• US 6261469 [0004]
• US Pat. No. 6710366 [0004]
• US 7341774 [0005]
• US 7387851 [0022]

Cited non-patent literature

• CB Murray, CR Kagan and MG Bawendi, Annu. Rev. Mater. Sci., 2000, 30, 545 [0019]
• CB Murray, DJ Norris and MG Bawendi, J. Am. Chem. Soc., 1993, 115, 8706 [0019]
• JE Bowen Katari, VL Colvin and AP Alivisatos, J. Phys. Chem., 1994, 98, 4109 [0019]
• MA Hines and P. Guyot-Sionnest, J. Phys. Chem., 1996, 100, 468 [0019]
• Bruchez Jr., M., Moronne, M., Gin, P., Weiss, S. & Alivisatos, AP Science, 1998, 281, 2013-2016 [0020]
• Chan, WCW & Nie, S. Science, 1998, 281, 2016-2018 [0020]

Claims (14)

A bicontinuous interpenetrating composite comprising: a semiconductive organic phase; a semiconducting particle phase; and a plurality of p-n junctions at interfaces between the semiconducting organic phase and the semiconducting particle phase; wherein the semiconductive organic phase and the semiconductive particle phase are interpenetrating and bicontinuous. The bicontinuous interpenetrating composite of claim 1, wherein the semiconducting organic phase is either a p-type organic semiconductor or an n-type organic semiconductor. The bicontinuous interpenetrating composite of claim 2, wherein the semiconductive organic phase is a p-type organic semiconductor and the semiconductive particle phase is an n-type particle semiconductor. The bicontinuous interpenetrating composite of claim 2, wherein the semiconductive organic phase is an n-type organic semiconductor and the semiconductive particle phase is a p-type particle semiconductor. A bicontinuous interpenetrating composite according to any one of the preceding claims, wherein the p-n junctions comprise a phenylene bonded to the particle phase. A bicontinuous interpenetrating composite according to any one of the preceding claims, further comprising a processing aid. A bicontinuous interpenetrating composite according to any one of the preceding claims, wherein the semiconductive particle phase comprises a plurality of particles having different band gaps. A bicontinuous interpenetrating composite according to any one of the preceding claims, wherein the semiconducting particle phase comprises a plurality of particles having a diameter of 1 nm to 500 nm or of 1 nm to 100 nm. A bicontinuous interpenetrating composite according to any one of the preceding claims, wherein the semiconductive particle phase comprises a first plurality of particles and a second plurality of particles, wherein the first plurality of particles has an amount of surface treatment greater than the second plurality of particles , Photovoltaic device comprising: a conductive front contact a conductive rear contact; and The bicontinuous interpenetrating composite of any one of the preceding claims is disposed between the front contact and the rear contact. A photovoltaic device according to claim 10, further comprising: an n-type layer and a p-type layer; wherein the bicontinuous interpenetrating composite is disposed between the n-type layer and the p-type layer. A method of making the bicontinuous interpenetrating composite according to any one of the preceding claims, comprising: Admixing an organic polymer, a first plurality of particles, and a second plurality of particles; wherein the first plurality of particles has an amount of surface treatments greater than the second plurality of particles. The method of claim 12, wherein admixing the organic polymer comprises admixing the first plurality of particles and the second plurality of particles to a liquid monomer and then polymerizing the monomer. The method of claim 13, wherein admixing the organic polymer comprises admixing the first plurality of particles and the second plurality of particles to a liquid monomer, a solvent, and a processing aid, and then polymerizing the monomer.

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