CN1719623A - Deep submicron 3-D heterojunction boundary for polymer solar battery and preparing process - Google Patents
Deep submicron 3-D heterojunction boundary for polymer solar battery and preparing process Download PDFInfo
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- CN1719623A CN1719623A CNA2005100427760A CN200510042776A CN1719623A CN 1719623 A CN1719623 A CN 1719623A CN A2005100427760 A CNA2005100427760 A CN A2005100427760A CN 200510042776 A CN200510042776 A CN 200510042776A CN 1719623 A CN1719623 A CN 1719623A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
This invention discloses a structure of a 3-D heterojunction interface of deep sub-micrometer of a polymer solar energy cell (PSC) and its manufacturing step. The character of the PSC is: the cross sections of the contact surfaces of P donor polymer semiconductor film and n acceptor polymer semiconductor film are inlaid with each other in a ladder type to make up of heterojunction interface of deep sub-micrometer 3-D shape, the combined size of the interface can greatly increase the PSC photoelectric conversion effect. The manufacture technology characterizes that the P type polymer material is a thermoplastic polymer semiconductor, the deep sub-micrometer 3-D structure on it is formed by heating and pressing a Ni die set to formation, the liquid n type polymer is set in vacuum after being coated and filled in the deep sub-micrometer structure on the p-type polymer to be heated or cured at room temperature.
Description
Technical field
The invention belongs to the micro-fabrication technology field, particularly a kind of version, preparation method and process materials key element that is used to improve the deep submicron 3-D heterojunction boundary of polymer solar battery (PSC-polymer solar cells) photoelectric conversion efficiency.
Background technology
Conventional solar cell is mainly made by mineral-type semiconductor (as silicon-based semiconductor) material, and existing numerous physical structure and manufacture methods is referred to as inorganic solar cell.Polymer solar battery (PSC-polymer solar cells) is mainly constituted by principal mode polymer semiconductor (being called for short n type polymer) by electron donor's type polymer semiconductor (being called for short p type polymer) with electronics, be that the electron donor is organic semiconductor compound with being subjected to the master, so also claim the organic semiconductor solar cell.Two base polymer semi-conducting materials are combined, can obtain to be similar to the such electrical characteristic of mineral-type semiconductor p-n junction.The contact position (interface) of p type polymer and n type polymer forms so-called " heterojunction " (heterojunction), near the heterojunction electronics or hole see through heterojunction and make directional migration and produce " photovoltaic " electric current (i.e. generating is referring to Fig. 2 b) under the photoinduction effect.Compare with the manufacturing of conventional mineral-type solar cell, the manufacturing process of PSC does not need to relate to expensive physics or chemical process means such as thin-film techniques such as inorganic matter sputter, evaporation, CVD, high purity silicon crystal growth preparation, doping.The advantage of PSC is: the raw material of p type polymer and n type polymer are synthetic, polymer is coated with the shop or depositing operation is simple, and cost is far below the physics or the chemical process means of inorganic matter; And PSC has very big flexibility, is fit to be made into non-flat board-like shape (for example, PSC directly can be produced on the curved surface shape covering of solar telephone).At present, the best photoelectric conversion efficiency that obtains under laboratory condition of PSC is only below 6%.But, after the photoelectric conversion efficiency of PSC reaches more than 8%, can replace existing inorganic solar cell and obtain to use widely according to external measuring and calculating.Therefore, the photoelectric conversion efficiency of raising PSC is its key that obtains large-scale industrial application.
The photoelectric conversion efficiency of PSC depends on preparation, the combination selection of p type polymer and n type polymer itself on the one hand.These aspects have numerous patent or open achievements in research.On the other hand, the photoelectric conversion efficiency of PSC also depends on the effective area of heterojunction boundary.
Therefore, the present invention proposes to make three-dimensional microstructures on p type polymer, enlarge the actual interfacial area (actual interface area) of p type polymer and n type polymer heterojunction, increase the area of space that the photoinduction electric charge takes place in the heterojunction, improve actual photoelectric conversion efficiency (referring to Fig. 1).The heterojunction boundary that the present invention relates to is shaped as the three-dimensional structure of deep-submicron, conventional machining mode can't realize, photoetching and etching cost commonly used in the integrated circuit fabrication process are too high, and may produce undesirable modification to p type polymer or n type polymer.Therefore, the present invention also announces relevant manufacture craft at the heterojunction boundary structure that is proposed.
Summary of the invention
The present invention is a purpose to improve photoelectric conversion efficiency, proposes PSC heterojunction boundary deep submicron 3-D structure and comprises the combination manufacture craft of the PSC of this heterojunction boundary structure.
The technical solution that realizes the foregoing invention purpose is: the polymer solar battery heterojunction comprises a kind of three-dimensional structure of deep-submicron yardstick.This polymer solar battery general structural features in mind is: transparent substrate 7 tops are provided with transparent metal positive electrode 6, anodal energy level regulating course 5, p type polymer film layer 4, n type polymer film layer 3, negative pole energy level regulating course 2, metal negative electrode 1 successively.Wherein, trapezoidal each other inlaying between the contact-making surface of p type thin polymer film 4 and n type thin polymer film 3, trapezoidal yardstick is the deep-submicron rank, thereby constitutes the p-n polymer heterojunction boundary of deep submicron 3-D shape.
The geometric properties of described deep submicron 3-D heterojunction boundary is for (referring to Fig. 2 a): the cross sectional shape of heterojunction boundary is trapezoidal, and the gradient α of trapezoidal sidewall is less than 80 °, and depth-to-width ratio is greater than 2, and the width at trapezoidal bottom and top is all less than 500nm.So can obtain the highest interfacial area increases than the ratio of solar panel projected area (the actual interfacial area with) and minimum electric charge secondary complex effect.
The above-mentioned polymer solar battery that contains deep submicron 3-D heterojunction boundary, its manufacture method comprise following preparation steps (referring to Fig. 3):
(1) in vacuum evaporation plating machine, transparent metal positive electrode 6 (as the ITO indium tin oxide) is deposited on the transparent substrates film 7 (as transparent polymethyl methacrylate material);
(2) on transparent metal positive electrode 6 surfaces, apply one deck energy level with shop glue machine or manual brushing mode and regulate material 5 (as polymer P EDOT), and make it under room temperature or heated condition, to solidify, form the anodal energy level regulating course of metal-polymer;
(3) be coated on the surface of anodal energy level regulating course 5 with p type polymer 4 materials (as MEH-PPV) of shop glue machine, and make it nature levelling and room temperature or be heating and curing liquid state;
(4) metal nickel mould that adopts the surface to comprise the deep submicron 3-D structure (flat or pulley type-Fig. 2 a), and heats it, impress out the deep submicron 3-D structure on p type polymer 4 material that solidified;
(5) comprising liquid n type polymer 3 thin layers of coating on the p type polymeric material 4 of deep submicron 3-D structure (as Alq with spraying cloth glue machine
3).Before the liquid n type polymer cure, whole semi-finished product are put into pressure vessel (using the pressurization of nitrogen or other inert gas), make liquid n type polymer fill the deep submicron 3-D structure that flows to p type polymer surfaces.After this, make liquid n type polymer levelling and curing in room temperature or heated condition;
(6) the n type in levelling curing is subjected to host polymer semiconductor film layer upper surface, with vacuum coating equipment evaporation last layer metal-polymer interface negative pole energy level regulating course 2 (as the Mg material), evaporation layer of metal film 1 (as AlMg) again on this metal-polymer interface negative pole energy level regulating course forms the negative electrode metal level then.
Wherein step (3), (4), (5) are the key that novel heterojunction boundary of the present invention is made.
The deep submicron 3-D heterojunction boundary and the preparation method of polymer semiconductor of the present invention solar cell, the useful technique effect that brings is as described below:
The heterojunction boundary of existing PSC is a planar structure, and effectively opto-electronic conversion area maximum is no more than the projected area of battery block.Adopt existing any polymer semiconductor material, the PSC photoelectric conversion efficiency of this planar structure is still less than 6%.Because thermoplastic imprint process method can copy the structure of nanoscale, method disclosed by the invention can be with (the live width yardstick L＜500nm of the deep submicron 3-D structure on the metal nickel mould, skew wall inclination alpha＜80 °, depth-to-width ratio H/L＞2) be transferred on the p type thin polymer film (any be thermoplastic p type thin polymer film semi-conducting material), (trapezoidal depth-to-width ratio is big more to make the effective interfacial area of p type polymer and n type polymer improve 3～5 times, effect is remarkable more), improve the effective area that opto-electronic conversion takes place greatly, thereby improved photoinduction charge density.In addition, its cross section of heterojunction boundary deep submicron 3-D structure that the present invention proposes is a trapezoidal shape, sidewall inclination alpha＜80 wherein °.This condition can guarantee: when increasing substantially the heterojunction boundary effective area, the electric charge secondary that is unlikely to significantly to increase groove place in the heterojunction is compound, thereby makes and do not give a discount because of interfacial area increases the photoelectric conversion efficiency that improves.
Generally speaking, use suitable mould, the hot padding process can be carried out primary transfer to 100nm, the structure depth-to-width ratio thermoplastic greater than 2, below area 150cm * 150cm to characteristic size is little, the transfer printing time is less than 1min, 120～180 ℃ of transfer printing temperature, the pressure of transfer process is less than 2000N.Because most p type polymeric materials just in time present thermoplasticity at solid state, the deep submicron 3-D structure among the present invention can realize according to said method fully.
With regard to production efficiency, be example with the battery block of 1 area in square inches, manufacture method of the present invention can realize the making of the three-dimensional structure heterojunction boundary that the 3000/min piece is above.
Description of drawings
Accompanying drawing 1 is a deep submicron 3-D heterojunction boundary cross section trapezium structure schematic cross-section.Label among the figure is represented respectively: 1 is metal negative electrode (as AlMg) film, and 2 is metal-polymer interface negative pole energy level regulating course (as the Mg film), and 3 is that n type polymer is (as Alq
3) film, 4 is p type polymer (as MEH-PPV) film, and 5 is anodal energy level regulating course (as PEDOT), and 6 is transparent metal positive electrode (as ITO) layer, and 7 is transparent substrates (as organic glass).Wherein, trapezoidal each other inlaying between the contact-making surface of p type thin polymer film 4 and n type thin polymer film 3, trapezoidal yardstick is the deep-submicron rank, thereby constitutes the p-n polymer heterojunction boundary of deep submicron 3-D shape.
Fig. 2 a is the schematic cross-section with metal nickel mould of deep submicron 3-D structure, so the deep submicron 3-D structure of p type polymer is its anti-shape.Wherein: the feature size L of metal nickel mould＜500nm; 8 is the supportive backing (for example steel) of mould among Fig. 2 a; 9 for comprising the mould (nickel) of deep submicron 3-D structure; The cross section of deep submicron 3-D structure is trapezoidal, its depth-to-width ratio H/L 〉=2, the inclination alpha of trapezoidal sidewall≤80 °.
Fig. 2 b is the PSC operation principle schematic diagram that comprises deep submicron 3-D heterojunction boundary.3 is n type thin polymer film, and 4 is p type thin polymer film, and 10 is sunlight, h
+Be the hole, e
-Be electronics.3 and 4 junction constitutes deep submicron 3-D heterojunction boundary.
Fig. 3 is PSC combination manufacture craft.1 is the negative electrode metal level, 2 is the energy level regulating course film of metal-polymer interface, 3 are subjected to the main semiconductor thin layer for the n type, 4 is p type polymer, and 5 is anodal energy level regulating course, and 6 is the transparent metal positive electrode, 7 is transparent substrates, 8 is the substrate backing of mould, and 9 is the deep submicron 3-D structure mold, and 11 is hot-fluid.Fig. 3 a is PSC positive electrode preparation technology, Fig. 3 b is the even adhesive process of PSC energy level regulating course preparation, Fig. 3 c is the equal adhesive process of p type polymeric layer, Fig. 3 d is metal die printed and formed deep submicron 3-D structural manufacturing process of hot pressing on p type polymeric material of deep submicron 3-D structure, Fig. 3 e is a releasing process, Fig. 3 f is a n type polymer semiconductor film spraying cloth adhesive process, and Fig. 3 g is the energy level regulating course film and the negative electrode metal level technology of evaporation metal-polymer interface.
The present invention is described in further detail below in conjunction with embodiment that accompanying drawing and operation principle and inventor provide.
Embodiment
The dark industry micron of the PSC that the present invention proposes 3-D heterojunction boundary cross section trapezium structure is referring to Fig. 1.Comprise transparent substrate 7, transparent substrate 7 tops are provided with transparent metal positive electrode 6, anodal energy level regulating course 5, p type polymer 4, n type polymer 3, metal-polymer interface negative pole energy level regulating course 2, metal negative electrode 1 successively.Wherein trapezoidal each other between p type thin polymer film 4 and n type thin polymer film 3 contact-making surfaces, constitute deep submicron 3-D heterojunction boundary.
The optional Mg of material of the optional AlMg of the material of metal negative electrode 1, metal-polymer interface negative pole energy level regulating course 2, the optional Alq of material of n type thin polymer film 3
3, the optional MEH-PPV of p type thin polymer film 4 materials (Poly 2 methoxy 5 (2 ' ethyl hexyloxy) 1,4 phenylvinylene), the optional PEDOT of anodal energy level regulating course 5 materials (Poly 3,4 ethylenedioxythiophene), the optional ITO of transparent metal positive electrode (Indium tin oxide), substrate backing 7 can be transparent organic glass class material.
Referring to Fig. 2 b, comprising: 3 is that n type thin polymer film, 4 is that p type thin polymer film, 10 is sunlight, h
+Be hole, e
-Be electronics.Deep submicron 3-D heterojunction boundary cross section micro-structural is referring to Fig. 2 a, the depth-to-width ratio H/L of micro-structural 〉=2, minimum feature size L＜500nm.
The operation principle of PSC is referring to Fig. 2 b, and under the induction of sunlight 10, the electronics of micel separates in the p type polymer 4, produces hole (h
+) and electronics (e
-) right, electric charge through energy level transition, is assembled positive and negative electric charge on positive electrode and negative electrode thin layer in heterojunction, form electromotive force, produces continuous current by external loop and load again.
Conventional PSC heterojunction boundary only is the plane combination of two layers of polymers semiconductive thin film.Compare with the heterojunction boundary on this plane, the real area of the deep submicron 3-D structure heterojunction boundary that the present invention proposes will increase by 4～6 times, increases substantially the generation rate of photoinduction charge density in the heterojunction; The tilt angle alpha of trapezoid micro-structure≤80 °.This condition can guarantee: when increasing substantially the heterojunction boundary effective area, the electric charge groove secondary that is unlikely to significantly to increase in the heterojunction is compound, thereby makes and not give a discount because of interfacial area increases the photoelectric conversion efficiency that improves.
Method of the present invention may further comprise the steps the preparation process of certain typical PSC:
(1) PSC positive electrode preparation.Be deposited on the transparent polymethyl methacrylate base material with the indium tin oxide (ITO) of commercially available evaporator, form the PSC positive electrode electrically conducting transparent;
(2) the anodal energy level regulating course preparation of PSC.With commercially available sol evenning machine the PEDOT polymer is coated with and is layered on the ITO surface, treat behind its natural levelling again through room temperature or be heating and curing, form the anodal energy level regulating course of metal-polymer;
(3) p type polymeric layer preparation.With commercially available equal glue machine p type polymeric material MEH-PPV is brushed the PEDOT surface, treat behind its natural levelling again through room temperature or be heating and curing;
(4) making of p type polymer surfaces deep submicron 3-D structure.Employing contains the metal nickel mould of deep submicron 3-D structure, and after it is heated to 120～180 ℃, presses to p type polymer MEH-PPV, obtains the anti-shape of mould deep submicron 3-D structure at this p type polymer surfaces;
(5) demoulding.After the mold cools down, afterburning with it disengaging p type polymer; Deep submicron 3-D structure on the p type polymer is formalized;
(6) comprising the liquid n type polymer film layer Alq of coating on the p type polymeric material of deep submicron 3-D structure with spraying cloth glue machine
3Before the liquid n type polymer cure, whole semi-finished product are put into pressure vessel (using the pressurization of nitrogen or other inert gas), make liquid n type polymer fill the deep submicron 3-D structure that flows to p type polymer surfaces.After this, make liquid n type polymer levelling and curing in room temperature or heated condition;
(7) the n type in levelling curing is subjected to host polymer semiconductor film layer upper surface, with vacuum coating equipment evaporation last layer metal-polymer interface negative pole energy level regulating course 2 (as the Mg material), evaporation layer of metal film 1 (as AlMg) again on this metal-polymer interface negative pole energy level regulating course forms the negative electrode metal level then.
Claims (5)
1. the structure of the deep submicron 3-D heterojunction boundary of polymer semiconductor's solar cell, comprise a transparent substrate, it is characterized in that, transparent substrate top is coated with successively and is covered with transparent metal positive electrode, the anodal energy level regulating course of metal-polymer, p type polymer, n type polymer, metal-polymer negative pole energy level regulating course, metal negative electrode, wherein, contact-making surface between p type polymer and the n type polymer is inlayed on microcosmic each other, constitutes deep submicron 3-D heterojunction boundary.
2. structure as claimed in claim 1, it is characterized in that: wherein the cross sectional shape of deep submicron 3-D structure heterojunction boundary is trapezoidal, its size combinations is: the gradient α of trapezoidal sidewall is less than 80 °, and depth-to-width ratio is greater than 2.0, and the width at trapezoidal bottom and top is all less than 500nm.
3. the preparation method of the deep submicron 3-D heterojunction boundary of polymer semiconductor's solar cell.It is characterized in that, comprise following preparation process:
(1) with shop glue machine the p type polymeric material of liquid state is coated to and makes on the complete anodal energy level regulating course surface, and make it nature levelling and room temperature or be heating and curing;
(2) adopt tabular or the cylinder shape metal die that comprises the deep submicron 3-D structure on the surface, on the p type polymeric material that has solidified, add hot padding, form the deep submicron 3-D structure of trapezoidal shape;
(3) comprising the liquid n type polymer film layer of coating on the p type surface of polymer material of deep submicron 3-D structure with injecting type cloth glue machine, before the n of liquid state type polymer cure, whole semi-finished product are put into pressure vessel, use the pressurization of nitrogen or other inert gases, make liquid n type polymer fill the deep submicron 3-D structure of having solidified on the p type polymer surfaces; After this, make liquid n type polymer levelling and curing in room temperature or heated condition.
4. method as claimed in claim 3 is characterized in that: described p type polymeric material is thermal plastic polymer's semiconductor; Deep submicron 3-D structure above it adopts the metal nickel mould heating and pressurizing to be shaped, i.e. thermoplastic forming.
5. method as claimed in claim 3 is characterized in that: insert in the vacuum environment after the n type of described liquid state is polymer-coated, make it to insert the deep submicron 3-D structure on the p type polymer after, again in room temperature or be heating and curing.
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Cited By (3)
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| CN102544376A (en) * | 2012-01-09 | 2012-07-04 | 浙江大学 | Polymer solar cell with subwavelength anti-reflective structure and manufacturing method for polymer solar cell |
| CN107195780A (en) * | 2017-06-03 | 2017-09-22 | 芜湖乐知智能科技有限公司 | A kind of one-dimensional position sensor and its manufacture method |
| JP2021177549A (en) * | 2015-02-26 | 2021-11-11 | ダイナミック ソーラー システムズ アクツィエンゲゼルシャフトDynamic Solar Systems Ag | Method for producing pv thin layers at room temperature and pv thin layer sequence obtained following the method |
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| JP4419357B2 (en) * | 2001-10-17 | 2010-02-24 | Ｊｓｒ株式会社 | Silane composition and method for producing solar cell using the same |
| KR100627203B1 (en) * | 2001-08-14 | 2006-09-22 | 제이에스알 가부시끼가이샤 | Silane Composition, Method for Forming a Silicone Film, and Method for Manufacturing Solar Cell |
| US7455955B2 (en) * | 2002-02-27 | 2008-11-25 | Brewer Science Inc. | Planarization method for multi-layer lithography processing |
| US7291782B2 (en) * | 2002-06-22 | 2007-11-06 | Nanosolar, Inc. | Optoelectronic device and fabrication method |
| US7462774B2 (en) * | 2003-05-21 | 2008-12-09 | Nanosolar, Inc. | Photovoltaic devices fabricated from insulating nanostructured template |
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| CN102544376A (en) * | 2012-01-09 | 2012-07-04 | 浙江大学 | Polymer solar cell with subwavelength anti-reflective structure and manufacturing method for polymer solar cell |
| CN102544376B (en) * | 2012-01-09 | 2014-06-04 | 浙江大学 | Polymer solar cell with subwavelength anti-reflective structure and manufacturing method for polymer solar cell |
| JP2021177549A (en) * | 2015-02-26 | 2021-11-11 | ダイナミック ソーラー システムズ アクツィエンゲゼルシャフトDynamic Solar Systems Ag | Method for producing pv thin layers at room temperature and pv thin layer sequence obtained following the method |
| CN107195780A (en) * | 2017-06-03 | 2017-09-22 | 芜湖乐知智能科技有限公司 | A kind of one-dimensional position sensor and its manufacture method |
| CN107195780B (en) * | 2017-06-03 | 2019-06-11 | 南京奇崛电子科技有限公司 | A kind of one-dimensional position sensor and its manufacturing method |
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