CN102692445A - Organic semiconductor gas sensor with organic heterojunction-containing gas-sensitive layer - Google Patents
Organic semiconductor gas sensor with organic heterojunction-containing gas-sensitive layer Download PDFInfo
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- CN102692445A CN102692445A CN201110073330XA CN201110073330A CN102692445A CN 102692445 A CN102692445 A CN 102692445A CN 201110073330X A CN201110073330X A CN 201110073330XA CN 201110073330 A CN201110073330 A CN 201110073330A CN 102692445 A CN102692445 A CN 102692445A
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Abstract
The invention provides an organic semiconductor gas sensor with an organic heterojunction-containing gas-sensitive layer, wherein the heterojunction is formed by charge transfer between two organic semiconductor materials, the redox potential on a film surface is changed, and thus the response of the sensor to sensitive gas is improved; the organic semiconductor gas sensor with the organic heterojunction-containing gas-sensitive layer provided by the invention has high sensitivity at room temperature, and a low gas-sensitive layer thickness, which effectively shortens the response/reply time of the device; the preparation of the device is completed once by a vacuum deposition method, and no subsequent process such as annealing and the like is required, which simplifies the preparation process of the device; The organic semiconductor gas sensor with the organic heterojunction-containing gas-sensitive layer provided by the invention can detect NO2 gas with a volume fraction of five parts per million, and the response/reply can be completed within 10 min.
Description
Technical field
The present invention relates to the organic semiconductor gas transducer that gas sensing layer contains organic heterojunction.
Technical background
Be accompanied by the development of organic semiconductor science and technology, scientist finds that a lot of organic semiconducting materials are to some toxic and harmfuls, like NO
2Deng having very responsive response, adopt the sensor of this type of material preparation to have high sensitivity.People such as B.Bott (B.Bott and T.A.Jones Sensors and Actuators 1984,5,43) have reported organic semiconducting materials phthalocyanine lead more than 100 ℃ the time, are part per billion NO in volume fraction
2Thin-film electro is led in the environment can obviously increase.This type of sensor is worked under hot environment usually, has limited its range of application.Therefore it is imperative to develop the sensor that can under room temperature environment, detect.People such as M.Passard (M.Passard, A.Pauly, J.P.Blanc, S.Dogo; J.P.Germain, C.Maleysson, Thin Solid Films, 1994; 237, discover that 272-276) different gas molecules is because redox characteristic is different; By after the phthalocyanine thin film absorption oxidation or reduction reaction can be taken place, produce free hole charge carrier or electronic carrier in the film, so thin-film electro is led and is changed.People such as T.Someya (T.Someya, H.E.Katz, A.Gelperin; A.J.Lovinger and A.Dodabalapur; Applied.Physics.Letter.2002,81,3079-3081) research and proposition; The absorption position of organic gas-sensitive film and gas is mainly at the crystal boundary place, and the polycrystal film that therefore has relatively large specific surface area is always by broad research.But the surface of polycrystalline membrane anisotropy is serious, and the activation energy wider distribution that the gas absorption of film surface active site-desorption process needs, desorption speed receive at a slow speed that active site influences seriously.The bigger polycrystalline film of these specific surface areas often realizes through thick film (0.5-1 micron), diffusion meeting significant prolongation sensor response time and the turnaround time of gas in thin-film body under the room temperature.Ultrathin membrane can realize that room temperature responds fast, and the VOPc ultrathin membrane can detect 100,000/NO under the room temperature
2And obviously increase at the high concentration gas sensitivity.The ultrathin membrane surface potential distributes and relatively evenly concentrates, and the crystal boundary number is less, and under the room temperature, 5/1000000ths following light concentration gas sensitivity are not high.Therefore, the redox-potential on adjusting organic semiconductor thin-film surface makes it to take place more easily and between the sensitive gas effective means that the electric charge transfer is a raising organic semiconductor gas transducer performance.2005, people such as Wang Jun (J.Wang, H.B.Wang, X.J.Yan, H.C.Hang, D.H.Yan, Applied Physics Letters, 2005,87,093507) reported two kinds of organic semiconductor interface accumulation free carriers, form heterojunction.The accumulation of free carrier causes the heterojunction boundary place to exist higher electricity to lead, and causes that simultaneously the position of two kinds of organic semi-conductor conduction bands in heterojunction boundary place and valence band changes.Promptly can change the redox-potential of material, thereby improve the susceptibility of material gas through the Heterojunction Effect between the organic semiconductor.People such as Zhu Feng (F.Zhu, J.B.Yang, D.Song; C.H.Li; D.H.Yan.Appl.Phys.Lett.2009,94,143305) find; Adopt in the organic heterojunction of weak epitaxial growth method preparation, the change of this redox-potential that is caused by Heterojunction Effect can be goed deep near the zone of the 40 nanometers heterojunction boundary.
Summary of the invention
The purpose of this invention is to provide the organic semiconductor gas transducer that gas sensing layer contains organic heterojunction.
Principle of the present invention is to utilize electric charge transfer formation heterojunction takes place between two kinds of organic semiconducting materials, changes the redox-potential of film surface, thereby improves the response of sensor to sensitive gas.
The organic semiconductor gas transducer that gas sensing layer provided by the invention contains organic heterojunction comprises that first kind of gas sensing layer contains the organic semiconductor gas transducer of organic heterojunction and the organic semiconductor gas transducer that second kind of gas sensing layer contains organic heterojunction.
Fig. 1 is the structural representation that first kind of gas sensing layer the present invention relates to contains the organic semiconductor gas transducer of organic heterojunction.
(A) first kind of gas sensing layer of the present invention contains being constructed as follows of organic semiconductor gas transducer of organic heterojunction: substrate 1, inducing layer 2, first organic semiconductor layer 3, second organic semiconductor layer 4 connect in order; The film of second organic semiconductor layer 4 is discontinuous film, and metal electrode 5 parts cover second organic semiconductor layer, 4 backs and connect with first organic semiconductor layer, the 3 corresponding parts that have; There is weak epitaxial relationship between the said inducing layer 2 and first organic semiconductor layer 3; Acting force between the material molecule that described weak epitaxial relationship is an inducing layer 2 and the material molecule of first organic semiconductor layer 3 is a Van der Waals force, and has epitaxial relationship between two kinds of molecular crystal lattices; Owing to shifting, electric charge forms heterojunction between described first organic semiconductor layer 3 and second organic semiconductor layer, 4 materials;
Described substrate 1 is an insulating material, and it is glass or pottery, or the compound substance that forms at conductive material surface coverage one deck insulating material, and it be the heavy mixed silicon slices in surface heat growth formation layer of silicon dioxide; If the r.m.s. roughness of substrate surface (RMS) is greater than 1 nanometer, the polymer coating of needs usefulness insulation such as polymethylmethacrylate (PMMA) or polyvinyl alcohol (PVA) (PVA) carry out smoothly;
Said inducing layer 2 is six biphenyl (p-6P), 2,7-two (4-xenyl)-Fei (BPPh), 2,5-two (4-1; 1 ': 4 ', 1 " terphenyl)-thiophene (3PT) and 2, a kind of among 7-two (4-4 '-fluorodiphenyl base)-Fei (F2-BPPh); thickness is not less than 2 nanometers, is not more than 10 nanometers;
Said first organic semiconductor layer 3 is metal-free phthalocyanine (H
2Pc) or containing metal phthalocyanine and functionalized variant thereof; Metallic phthalocyanine is a kind of in CuPc (CuPc), phthalocyanine nickel (NiPc), phthalocyanine cobalt (CoPc), ferrous phthalocyanine (FePc), Phthalocyanine Zinc (ZnPc), phthalocyanine plumbous (PbPc) and the phthalocyanine tin (SnPc); The functionalized variant of metallic phthalocyanine is ranadylic phthalocyanine (VOPc), TiOPc (TiOPc), phthalocyanine chlorine aluminium (AlClPc), phthalocyanine dichloro tin (SnCl
2Pc), phthalocyanine oxygen tin (SnOPc), perfluoro CuPc (F
16CuPc), perfluoro Phthalocyanine Zinc (F
16ZnPc) and perfluoro phthalocyanine cobalt (F
16CoPc) a kind of in; Its thickness is not less than 1.5 nanometers, is not more than 20 nanometers;
Described second organic semiconductor layer 4 is metal-free phthalocyanine (H
2Pc) or containing metal phthalocyanine and functionalized variant thereof; Metallic phthalocyanine is a kind of in CuPc (CuPc), phthalocyanine nickel (NiPc), phthalocyanine cobalt (CoPc), ferrous phthalocyanine (FePc), Phthalocyanine Zinc (ZnPc), phthalocyanine plumbous (PbPc) and the phthalocyanine tin (SnPc); The functionalized variant of metallic phthalocyanine is ranadylic phthalocyanine (VOPc), TiOPc (TiOPc), phthalocyanine chlorine aluminium (AlClPc), phthalocyanine dichloro tin (SnCl
2Pc), phthalocyanine oxygen tin (SnOPc), perfluoro CuPc (F
16CuPc), perfluoro Phthalocyanine Zinc (F
16ZnPc) and perfluoro phthalocyanine cobalt (F
16CoPc) a kind of in; Its thickness is not less than 0.2 nanometer, is not more than 1.5 nanometers;
The material of metal electrode 5 is a gold.
Fig. 2 is the structural representation that second kind of gas sensing layer the present invention relates to contains the organic semiconductor gas transducer of organic heterojunction.
(B) second kind of gas sensing layer of the present invention contains being constructed as follows of organic semiconductor gas transducer of organic heterojunction: substrate 1, inducing layer 2, first organic semiconductor layer 3 connect in order; First organic semiconductor layer 3 all is connected with second organic semiconductor layer 4, metal electrode 5, and metal electrode 5 also has part directly to contact with first organic semiconductor layer 3; There is weak epitaxial relationship between the described inducing layer 2 and first organic semiconductor layer 3; Form heterojunction because of the electric charge transfer between described organic semiconductor layer 3 and the organic semiconductor layer 4; The film of second organic semiconductor layer 4 is discontinuous film;
The material of described substrate 1 and disposal route are with (A); The material of metal electrode 5 is with (A);
The material of described inducing layer 2, first organic semiconductor layer 3, second organic semiconductor layer 4 and thickness are with (A).
The organic semiconductor gas transducer that gas sensing layer involved in the present invention contains organic heterojunction can adopt the mode of planar diode to measure, and is about to metal electrode 5 and measures as the positive and negative electrode of diode respectively.For substrate is the compound substance that forms at conductive material surface coverage one deck insulating material, can also adopt transistorized mode to measure, and is about to conductive material as transistorized gate electrode, and electrode 5 is measured as transistorized source/drain electrode respectively.
The preparation method of organic semiconductor gas transducer that gas sensing layer of the present invention contains organic heterojunction is following:
(I) the organic semiconductor gas transducer method for making that the first kind of gas sensing layer that the present invention relates to contains organic heterojunction is following:
(1) substrate 1 is an insulating material, and it is glass or pottery, or the compound substance that forms at conductive material surface coverage one deck insulating material, and it be the heavy mixed silicon slices in surface heat growth formation layer of silicon dioxide; If the r.m.s. roughness of substrate surface (RMS) is greater than 1 nanometer, the polymer coating of needs usefulness insulation such as polymethylmethacrylate (PMMA) or polyvinyl alcohol (PVA) (PVA) carry out smoothly;
(2) at substrate 1 surface vacuum deposition inducing layer 2, thickness is not less than 2 nanometers, is no more than 10 nanometers; Material is six biphenyl (p-6P), 2; 7-two (4-xenyl)-Fei (BPPh), 2,5-two (4-1,1 ': 4 '; 1 " terphenyl)-and thiophene (3PT) and 2, a kind of among 7-two (4-4 '-fluorodiphenyl base)-Fei (F2-BPPh);
(3) deposit first organic semiconductive layer 3 at inducing layer 2 surface vacuums, thickness is not less than 1.5 nanometers, is not more than 20 nanometers; There is weak epitaxial relationship between the described inducing layer 2 and first organic semiconductor layer 3; Acting force between the material molecule that said weak epitaxial relationship is an inducing layer 2 and the material molecule of organic semiconductor layer 3 is a Van der Waals force, and has epitaxial relationship between two kinds of molecular crystal lattices; The material of first organic semiconductive layer 3 is metal-free phthalocyanine (H
2Pc) or containing metal phthalocyanine and functionalized variant thereof; Metallic phthalocyanine is a kind of in CuPc (CuPc), phthalocyanine nickel (NiPc), phthalocyanine cobalt (CoPc), ferrous phthalocyanine (FePc), Phthalocyanine Zinc (ZnPc), phthalocyanine plumbous (PbPc) and the phthalocyanine tin (SnPc); The functionalized variant of metallic phthalocyanine is ranadylic phthalocyanine (VOPc), TiOPc (TiOPc), phthalocyanine chlorine aluminium (AlClPc), phthalocyanine dichloro tin (SnCl
2Pc), phthalocyanine oxygen tin (SnOPc), perfluoro CuPc (F
16CuPc), perfluoro Phthalocyanine Zinc (F
16ZnPc) and perfluoro phthalocyanine cobalt (F
16CoPc) a kind of in;
(4) film that deposits second organic semiconductor layer, 4, the second organic semiconductor layers 4 at first organic semiconductor layer, 3 surface vacuums is discontinuous film; Because shifting, electric charge forms heterojunction between described second organic semiconductor layer 4 and first organic semiconductor layer, 3 materials; The thickness of described second organic semiconductor layer 4 is not less than 0.2 nanometer, is not more than 1.5 nanometers, and material is metal-free phthalocyanine (H
2Pc) or containing metal phthalocyanine and functionalized variant thereof; Metallic phthalocyanine is a kind of in CuPc (CuPc), phthalocyanine nickel (NiPc), phthalocyanine cobalt (CoPc), ferrous phthalocyanine (FePc), Phthalocyanine Zinc (ZnPc), phthalocyanine plumbous (PbPc) and the phthalocyanine tin (SnPc); The functionalized variant of metallic phthalocyanine is ranadylic phthalocyanine (VOPc), TiOPc (TiOPc), phthalocyanine chlorine aluminium (AlClPc), phthalocyanine dichloro tin (SnCl
2Pc), phthalocyanine oxygen tin (SnOPc), perfluoro CuPc (F
16CuPc), perfluoro Phthalocyanine Zinc (F
16ZnPc) and perfluoro phthalocyanine cobalt (F
16CoPc) a kind of in;
(5) utilize bushing vacuum deposited metal electrode 5 at second organic semiconductor layer, 4 part surfaces;
Wherein, the base vacuum degree is not less than 8.0 * 10
-4Pa, the metal electrode rate of sedimentation is 20 nm/minute, the rate of sedimentation of other materials is 1 nm/minute.
The thickness of organic semiconductor layer is by the decision of the product of rate of sedimentation and sedimentation time, and when the two product during less than characteristic thickness, the gained film is discontinuous film; The thickness of the characteristic that described second organic semiconductor layer, 4 employed materials form is all greater than 1.5 nanometers, and therefore the film of second organic semiconductor layer 4 of preparation is discontinuous film as stated above.
(II) the organic semiconductor gas transducer method for making that the second kind of gas sensing layer that the present invention relates to contains organic heterojunction is following:
(1) substrate 1 is an insulating material, and it is glass or pottery, or the compound substance that forms at conductive material surface coverage one deck insulating material, and it be in heavy mixed silicon slices surface heat growth formation layer of silicon dioxide; If the r.m.s. roughness of substrate surface (RMS) greater than 1 nanometer, needs to carry out smoothly with polymer coating such as the polymethylmethacrylate (PMMA) or the polyvinyl alcohol (PVA) (PVA) etc. of insulation;
(2) at substrate surface vacuum moulding machine inducing layer 2, thickness is not less than 2 nanometers, is no more than 10 nanometers; Material is six biphenyl (p-6P), 2; 7-two (4-xenyl)-Fei (BPPh), 2,5-two (4-1,1 ': 4 '; 1 " terphenyl)-and thiophene (3PT) and 2, a kind of among 7-two (4-4 '-fluorodiphenyl base)-Fei (F2-BPPh);
(3) deposit first organic semiconductive layer 3 at inducing layer 2 surface vacuums; There is weak epitaxial relationship between the said inducing layer 2 and first organic semiconductor layer 3; Thickness is not less than 1.5 nanometers; Be not more than 20 nanometers, the acting force between the material molecule that said weak epitaxial relationship is an inducing layer 2 and the material molecule of first organic semiconductor layer 3 is a Van der Waals force, and has epitaxial relationship between two kinds of molecular crystal lattices; The material of first organic semiconductive layer 3 is metal-free phthalocyanine (H
2Pc) or containing metal phthalocyanine and functionalized variant thereof; Metallic phthalocyanine is a kind of in CuPc (CuPc), phthalocyanine nickel (NiPc), phthalocyanine cobalt (CoPc), ferrous phthalocyanine (FePc), Phthalocyanine Zinc (ZnPc), phthalocyanine plumbous (PbPc) and the phthalocyanine tin (SnPc); The functionalized variant of metallic phthalocyanine is ranadylic phthalocyanine (VOPc), TiOPc (TiOPc), phthalocyanine chlorine aluminium (AlClPc), phthalocyanine dichloro tin (SnCl
2Pc), phthalocyanine oxygen tin (SnOPc), perfluoro CuPc (F
16CuPc), perfluoro Phthalocyanine Zinc (F
16ZnPc) and perfluoro phthalocyanine cobalt (F
16CoPc) a kind of in;
(4) part surface at first organic semiconductor layer 3 utilizes bushing vacuum deposited metal electrode 5;
(5) to deposit the film of second organic semiconductor layer, 4, the second organic semiconductor layers 4 be discontinuous film to the partial vacuum beyond the surperficial empty deposit metal electrodes of first organic semiconductor layer 35; Because shifting, electric charge forms heterojunction between described second organic semiconductor layer 4 and first organic semiconductor layer, 3 materials; The thickness of described second organic semiconductor layer 4 is not less than 0.2 nanometer, is not more than 1.5 nanometers, and the material of second organic semiconductor layer 4 is metal-free phthalocyanine (H2Pc) or containing metal phthalocyanine and functionalized variant thereof; Metallic phthalocyanine is a kind of in CuPc (CuPc), phthalocyanine nickel (NiPc), phthalocyanine cobalt (CoPc), ferrous phthalocyanine (FePc), Phthalocyanine Zinc (ZnPc), phthalocyanine plumbous (PbPc) and the phthalocyanine tin (SnPc); The functionalized variant of metallic phthalocyanine is ranadylic phthalocyanine (VOPc), TiOPc (TiOPc), phthalocyanine chlorine aluminium (AlClPc), phthalocyanine dichloro tin (SnCl
2Pc), phthalocyanine oxygen tin (SnOPc), perfluoro CuPc (F
16CuPc), perfluoro Phthalocyanine Zinc (F
16ZnPc) and perfluoro phthalocyanine cobalt (F
16CoPc) a kind of in;
Wherein, the base vacuum degree is not less than 8.0 * 10
-4Pa, the metal electrode rate of sedimentation is 20 nm/minute, the rate of sedimentation of other materials is 1 nm/minute.
The thickness of organic semiconductor layer is by the decision of the product of rate of sedimentation and sedimentation time, and when the two product during less than characteristic thickness, the gained film is discontinuous film.The thickness of the characteristic that described second organic semiconductor layer, 4 employed materials form is all greater than 1.5 nanometers, and therefore the film of second organic semiconductor layer 4 of preparation is discontinuous film as stated above.Because metal electrode has part second organic semiconductor 4 when therefore depositing second organic semiconductor layer 4 and is deposited on surface of metal electrode prior to second organic semiconductor layer, 4 depositions, this point can be ignored to the influence of device.
Beneficial effect: gas sensing layer provided by the invention contains the organic semiconductor gas transducer of organic heterojunction, comprises that first kind of gas sensing layer contains the organic semiconductor gas transducer device of organic heterojunction and the organic semiconductor gas transducer that second kind of gas sensing layer contains organic heterojunction.The organic semiconductor gas transducer that gas sensing layer provided by the invention contains organic heterojunction is to utilize electric charge transfer formation heterojunction takes place between two kinds of organic semiconducting materials; Change the redox-potential of film surface, thereby improve the response of sensor sensitive gas.It is high that gas sensing layer provided by the invention contains under the organic semiconductor gas transducer room temperature condition of organic heterojunction susceptibility; Gas sensing layer thickness is little; Effectively shortened the response/turnaround time of device; And utilize the disposable completion preparation of devices of vacuum deposition method, subsequent technique such as need not anneal has been simplified the preparation of devices process.The organic semiconductor gas transducer that gas sensing layer provided by the invention contains organic heterojunction can the detection volume mark be 5/1000000ths NO
2Gas, and response/answer all can be accomplished in 10 minutes.
Description of drawings
Fig. 1 is the structural representation that first kind of gas sensing layer the present invention relates to contains the organic semiconductor gas transducer of organic heterojunction.
Fig. 2 is the structural representation that second kind of gas sensing layer the present invention relates to contains the organic semiconductor gas transducer of organic heterojunction.
Fig. 3 is that to adopt the gas sensing layer that the present invention relates to of configuration shown in Figure 1 to contain under the organic semiconductor gas transducer room temperature of organic heterojunction be the response/return curve of millionth NO2 gas to volume fraction.Wherein, substrate is that Film by Thermal Oxidation forms SiO
2Heavy mixed silicon slices, inducing layer is p-6P, thickness 4 nanometers, organic semiconductor layer 3 is TiOPc, thickness 3 nanometers, machine semiconductor layer 4 is F
16CuPc, thickness 0.5 nanometer adopts gold as electrode.
Fig. 4 adopts the second kind of gas sensing layer that the present invention relates to of configuration shown in Figure 2 to contain under the organic semiconductor gas transducer room temperature of organic heterojunction at the NO that to volume fraction is 5/1000000ths
2Response/the return curve of gas.Wherein, substrate is the SiO of surface coverage one deck heat growth
2Heavy mixed silicon slices, inducing layer is p-6P, thickness 2 nanometers, organic semiconductor layer 3 is VOPc, thickness 2 nanometers, organic semiconductor layer 4 is CuPc, thickness 1 nanometer adopts gold as electrode.
Embodiment
Below adopt metal-free phthalocyanine (H among all embodiment
2Pc), CuPc (CuPc), phthalocyanine nickel (NiPc), phthalocyanine cobalt (CoPc), ferrous phthalocyanine (FePc); Phthalocyanine Zinc (ZnPc), phthalocyanine plumbous (PbPc), phthalocyanine tin (SnPc); Ranadylic phthalocyanine (VOPc), TiOPc (TiOPc), phthalocyanine chlorine aluminium (AlClPc), phthalocyanine dichloro tin (SnCl
2Pc), phthalocyanine oxygen tin (SnOPc), perfluoro CuPc (F
16CuPc), perfluoro Phthalocyanine Zinc (F
16ZnPc), perfluoro phthalocyanine cobalt (F
16CoPc), 2,7-two (4-xenyl)-Fei (BPPh), 2,5-two (4-1,1 ': 4 ', 1 " terphenyl)-thiophene (3PT), 2,7-two (4-4 '-fluorodiphenyl base)-Fei (F2-BPPh) is commercial product, buys after use behind the vacuum sublimation purification secondary.Glass, pottery, Film by Thermal Oxidation forms silicon dioxide (SiO
2) heavy mixed silicon slices, clean the back and use, polymethyl-benzene olefin(e) acid methyl esters (PMMA), polyvinyl alcohol (PVA) (PVA) is commercially produced product, buys directly use of back.
It is as shown in Figure 1 that first kind of gas sensing layer of the present invention contains the configuration of organic semiconductor gas transducer of organic heterojunction, and concrete preparation method is following:
(1) substrate 1 is an insulating material, and it is glass or pottery, or the compound substance that forms at conductive material surface coverage one deck insulating material, and it be the heavy mixed silicon slices in surface heat growth formation layer of silicon dioxide; If the r.m.s. roughness of substrate surface (RMS) is greater than 1 nanometer, the polymer coating of needs usefulness insulation such as polymethylmethacrylate (PMMA) or polyvinyl alcohol (PVA) (PVA) carry out smoothly;
(2) at substrate 1 surface vacuum deposition inducing layer 2, thickness is not less than 2 nanometers, is no more than 10 nanometers; Material is six biphenyl (p-6P), 2; 7-two (4-xenyl)-Fei (BPPh), 2,5-two (4-1,1 ': 4 '; 1 " terphenyl)-and thiophene (3PT) and 2, a kind of among 7-two (4-4 '-fluorodiphenyl base)-Fei (F2-BPPh);
(3) deposit first organic semiconductive layer 3 at inducing layer 2 surface vacuums, have weak epitaxial relationship between the said inducing layer 2 and first organic semiconductor layer 3; Acting force between the material molecule that said weak epitaxial relationship is an inducing layer 2 and the material molecule of organic semiconductor layer 3 is a Van der Waals force, and has epitaxial relationship between two kinds of molecular crystal lattices.Thickness is not less than 1.5 nanometers, is not more than 20 nanometers, and the material of first organic semiconductive layer 3 is metal-free phthalocyanine (H
2Pc) or containing metal phthalocyanine and functionalized variant thereof; Metallic phthalocyanine is a kind of in CuPc (CuPc), phthalocyanine nickel (NiPc), phthalocyanine cobalt (CoPc), ferrous phthalocyanine (FePc), Phthalocyanine Zinc (ZnPc), phthalocyanine plumbous (PbPc) and the phthalocyanine tin (SnPc); The functionalized variant of metallic phthalocyanine is ranadylic phthalocyanine (VOPc), TiOPc (TiOPc), phthalocyanine chlorine aluminium (AlClPc), phthalocyanine dichloro tin (SnCl
2Pc), phthalocyanine oxygen tin (SnOPc), perfluoro CuPc (F
16CuPc), perfluoro Phthalocyanine Zinc (F
16ZnPc) and perfluoro phthalocyanine cobalt (F
16CoPc) a kind of in;
(4) film that deposits second organic semiconductor layer, 4, the second organic semiconductor layers 4 at first organic semiconductor layer, 3 surface vacuums is discontinuous film; Because shifting, electric charge forms heterojunction between described second organic semiconductor layer 4 and first organic semiconductor layer, 3 materials; The thickness of described second organic semiconductor layer 4 is not less than 0.2 nanometer, is not more than 1.5 nanometers, and the material of second organic semiconductor layer 4 is metal-free phthalocyanine (H
2Pc) or containing metal phthalocyanine and functionalized variant thereof; Metallic phthalocyanine is a kind of in CuPc (CuPc), phthalocyanine nickel (NiPc), phthalocyanine cobalt (CoPc), ferrous phthalocyanine (FePc), Phthalocyanine Zinc (ZnPc), phthalocyanine plumbous (PbPc) and the phthalocyanine tin (SnPc); The functionalized variant of metallic phthalocyanine is ranadylic phthalocyanine (VOPc), TiOPc (TiOPc), phthalocyanine chlorine aluminium (AlClPc), phthalocyanine dichloro tin (SnCl
2Pc), phthalocyanine oxygen tin (SnOPc), perfluoro CuPc (F
16CuPc), perfluoro Phthalocyanine Zinc (F
16ZnPc) and perfluoro phthalocyanine cobalt (F
16CoPc) a kind of in;
(5) utilize bushing vacuum deposited metal electrode 5 at second organic semiconductor layer, 4 part surfaces; The material of metal electrode 5 is a gold;
Wherein, the base vacuum degree is not less than 8.0 * 10
-4Pa, the metal electrode rate of sedimentation is 20 nm/minute, the rate of sedimentation of other materials is 1 nm/minute.
The thickness of organic semiconductor layer is by the decision of the product of rate of sedimentation and sedimentation time, and when the two product during less than characteristic thickness, the gained film is discontinuous film; The thickness of the characteristic that described second organic semiconductor layer, 4 employed materials form is all greater than 1.5 nanometers, and therefore the film of second organic semiconductor layer 4 of preparation is discontinuous film as stated above.
Fig. 3 is that to adopt the first kind of gas sensing layer that the present invention relates to of configuration shown in Figure 1 to contain under the organic semiconductor gas transducer room temperature of organic heterojunction be millionth NO to volume fraction
2Response/the return curve of gas.Wherein, substrate is that Film by Thermal Oxidation forms SiO
2Heavy mixed silicon slices, inducing layer is p-6P, thickness 4 nanometers, organic semiconductor layer 3 is TiOPc, thickness 3 nanometers, machine semiconductor layer 4 is F
16CuPc, thickness 0.5 nanometer adopts gold as electrode.Compare with the reference device, the reference device is response not, and adopting the sensitivity of first kind of organic semiconductor gas transducer of structure shown in Figure 1 is 17,2.5 minutes response times, 7 minutes turnaround times.The described response time is to begin to reach peak value 50% required time to the current value of sensor from beginning logical NO2, and be to stop logical NO2 to begin to reduce to the required time of peak value 50% to the current value of sensor turnaround time.Therefore, response/turnaround time of device has been shortened in the sensitivity that the organic semiconductor gas transducer that adopts gas sensing layer of the present invention to contain organic heterojunction can effectively improve device.
Table 1 provided adopt above-mentioned technology and contain by first kind of gas sensing layer of the specified criteria of table 1 preparation organic heterojunction organic semiconductor gas transducer composition and at NO
2Volume fraction is 5/1000000ths o'clock device parameters.
Table 1
Annotate: SiO
2Be meant that Film by Thermal Oxidation forms SiO
2Heavy mixed silicon slices, sensitivity and after response/turnaround time mark * number be the data that adopt the transistor metering system to obtain, what all the other did not do to mark is the data that adopt the planar diode metering system to obtain.
The organic semiconductor gas transducer method for making that the second kind of gas sensing layer that the present invention relates to of structure as shown in Figure 2 contains organic heterojunction is following:
(1) substrate 1 is an insulating material, and it is glass or pottery, or the compound substance that forms at conductive material surface coverage one deck insulating material, and it be in heavy mixed silicon slices surface heat growth formation layer of silicon dioxide; If the r.m.s. roughness of substrate surface (RMS) is greater than 1 nanometer, the polymer coating of needs usefulness insulation such as polymethylmethacrylate (PMMA) or polyvinyl alcohol (PVA) (PVA) carry out smoothly;
(2) at substrate surface vacuum moulding machine inducing layer 2, thickness is not less than 2 nanometers, is no more than 10 nanometers; Material is six biphenyl (p-6P), 2; 7-two (4-xenyl)-Fei (BPPh), 2,5-two (4-1,1 ': 4 '; 1 " terphenyl)-and thiophene (3PT) and 2, a kind of among 7-two (4-4 '-fluorodiphenyl base)-Fei (F2-BPPh);
(3) deposit first organic semiconductive layer 3 at inducing layer 2 surface vacuums; There is weak epitaxial relationship between the said inducing layer 2 and first organic semiconductor layer 3; Acting force between the material molecule that said weak epitaxial relationship is an inducing layer 2 and the material molecule of first organic semiconductor layer 3 is a Van der Waals force, and has epitaxial relationship between two kinds of molecular crystal lattices; The thickness of first organic semiconductive layer 3 is not less than 1.5 nanometers, is not more than 20 nanometers, and material is metal-free phthalocyanine (H
2Pc) or containing metal phthalocyanine and functionalized variant thereof; Metallic phthalocyanine is a kind of in CuPc (CuPc), phthalocyanine nickel (NiPc), phthalocyanine cobalt (CoPc), ferrous phthalocyanine (FePc), Phthalocyanine Zinc (ZnPc), phthalocyanine plumbous (PbPc) and the phthalocyanine tin (SnPc); The functionalized variant of metallic phthalocyanine is ranadylic phthalocyanine (VOPc), TiOPc (TiOPc), phthalocyanine chlorine aluminium (AlClPc), phthalocyanine dichloro tin (SnCl
2Pc), phthalocyanine oxygen tin (SnOPc), perfluoro CuPc (F
16CuPc), perfluoro Phthalocyanine Zinc (F
16ZnPc) and perfluoro phthalocyanine cobalt (F
16CoPc) a kind of in;
(4) utilize bushing vacuum deposited metal electrode 5 at first organic semiconductor layer, 3 part surfaces; The material of metal electrode 5 is a gold;
(5) to deposit the film of second organic semiconductor layer, 4, the second organic semiconductor layers 4 be discontinuous film to the partial vacuum beyond the surperficial empty deposit metal electrodes of first organic semiconductor layer 35; Form heterojunction because electric charge shifts between described second organic semiconductor layer 4 and first organic semiconductor layer, 3 materials, the thickness of described second organic semiconductor layer 4 is not less than 0.2 nanometer, is not more than 1.5 nanometers, and material is metal-free phthalocyanine (H
2Pc) or containing metal phthalocyanine and functionalized variant thereof; Metallic phthalocyanine is a kind of in CuPc (CuPc), phthalocyanine nickel (NiPc), phthalocyanine cobalt (CoPc), ferrous phthalocyanine (FePc), Phthalocyanine Zinc (ZnPc), phthalocyanine plumbous (PbPc) and the phthalocyanine tin (SnPc); The functionalized variant of metallic phthalocyanine is ranadylic phthalocyanine (VOPc), TiOPc (TiOPc), phthalocyanine chlorine aluminium (AlClPc), phthalocyanine dichloro tin (SnCl
2Pc), phthalocyanine oxygen tin (SnOPc), perfluoro CuPc (F
16CuPc),, perfluoro Phthalocyanine Zinc (F
16ZnPc) and perfluoro phthalocyanine cobalt (F
16CoPc) a kind of in;
Wherein, the base vacuum degree is not less than 8.0 * 10
-4Pa, the metal electrode rate of sedimentation is 20 nm/minute, the rate of sedimentation of other materials is 1 nm/minute.
The thickness of organic semiconductor layer is by the decision of the product of rate of sedimentation and sedimentation time, and when the two product during less than characteristic thickness, the gained film is discontinuous film.The thickness of the characteristic that described second organic semiconductor layer, 4 employed materials form is all greater than 1.5 nanometers, and therefore the film of second organic semiconductor layer 4 of preparation is discontinuous film as stated above.Because metal electrode has part second organic semiconductor 4 when therefore depositing second organic semiconductor layer 4 and is deposited on surface of metal electrode prior to second organic semiconductor layer, 4 depositions, this point can be ignored to the influence of device.
The organic semiconductor gas transducer that the gas sensing layer that Fig. 4 provides structure shown in Figure 2 contains organic heterojunction is response/return curve of 5/1000000ths o'clock in the nitrogen dioxide volume fraction.Wherein, substrate is the SiO of surface coverage one deck heat growth
2Heavy mixed silicon slices, inducing layer is p-6P, thickness 2 nanometers, organic semiconductor layer 3 is VOPc, thickness 2 nanometers, organic semiconductor layer 4 is CuPc, thickness 1 nanometer adopts gold as electrode.Compare with the reference device, the reference device does not have response, and the organic semiconductor gas transducer sensitivity of adopting gas sensing layer provided by the invention to contain organic heterojunction is 10,2.5 minutes response times, 7 minutes turnaround times.The described response time is to begin to reach peak value 50% required time to the current value of sensor from beginning logical NO2, and be to stop logical NO2 to begin to reduce to the required time of peak value 50% to the current value of sensor turnaround time.Therefore, the sensitivity that the organic semiconductor gas transducer that adopts gas sensing layer of the present invention to contain organic heterojunction can effectively improve device, the response/turnaround time of reducing device.
Table 2 provided adopt above-mentioned technology and contain by second kind of gas sensing layer of the specified criteria of table 2 preparation organic heterojunction organic semiconductor gas transducer composition and at NO
2Volume fraction is 5/1000000ths o'clock device parameters.
Table 2
Annotate: SiO
2Be meant that Film by Thermal Oxidation forms silicon dioxide (SiO
2) heavy mixed silicon slices, sensitivity and after response/turnaround time mark * number be the data that adopt the transistor metering system to obtain, what all the other did not do to mark is the data that adopt the planar diode metering system to obtain.
Claims (5)
1. gas sensing layer contains the organic semiconductor gas transducer of organic heterojunction, it is characterized in that, comprises that first kind of gas sensing layer contains the organic semiconductor gas transducer of organic heterojunction and the organic semiconductor gas transducer that second kind of gas sensing layer contains organic heterojunction; (A) first kind of gas sensing layer contains being constructed as follows of organic semiconductor gas transducer of organic heterojunction: substrate (1), inducing layer (2), first organic semiconductor layer (3), second organic semiconductor layer (4) connect in order; The film of second organic semiconductor layer (4) is discontinuous film, and metal electrode (5) part covers second organic semiconductor layer (4) back the have part corresponding with first organic semiconductor layer (3) and connects; There is weak epitaxial relationship between said inducing layer (2) and first organic semiconductor layer (3); Acting force between the material molecule that described weak epitaxial relationship is an inducing layer (2) and the material molecule of first organic semiconductor layer (3) is a Van der Waals force, and has epitaxial relationship between two kinds of molecular crystal lattices; Owing to shifting, electric charge forms heterojunction between described first organic semiconductor layer (3) and second organic semiconductor layer (4); (B) second kind of gas sensing layer contains being constructed as follows of organic semiconductor gas transducer of organic heterojunction: substrate (1), inducing layer (2), first organic semiconductor layer (3) connect in order; First organic semiconductor layer (3) all is connected with second organic semiconductor layer (4), metal electrode (5), and metal electrode (5) also has part directly to contact with first organic semiconductor layer (3); There is weak epitaxial relationship between described inducing layer (2) and first organic semiconductor layer (3); Form heterojunction because of the electric charge transfer between described first organic semiconductor layer (3) and second organic semiconductor layer (4); The film of second organic semiconductor layer (4) is discontinuous film.
2. the organic semiconductor gas transducer that contains organic heterojunction by the described gas sensing layer of claim 1; It is characterized in that; Described substrate (1) is an insulating material; It is glass or pottery, or the compound substance that forms at conductive material surface coverage one deck insulating material, and it be the heavy mixed silicon slices in surface heat growth formation layer of silicon dioxide; If the r.m.s. roughness of substrate surface is greater than 1 nanometer, need carry out smoothly with the polymer coating of insulation such as polymethylmethacrylate or polyvinyl alcohol (PVA); Described inducing layer (2) is six biphenyl, 2,7-two (4-xenyl)-Fei, 2,5-two (4-1,1 ': 4 ', 1 " terphenyl)-thiophene) and 2, a kind of among 7-two (4-4 '-fluorodiphenyl base)-Fei; Described first organic semiconductor layer (3) is metal-free phthalocyanine or containing metal phthalocyanine and functionalized variant thereof; Metallic phthalocyanine is a kind of in CuPc, phthalocyanine nickel, phthalocyanine cobalt, ferrous phthalocyanine, Phthalocyanine Zinc, phthalocyanine lead and the phthalocyanine tin; The functionalized variant of metallic phthalocyanine is a kind of in ranadylic phthalocyanine, TiOPc, phthalocyanine chlorine aluminium, phthalocyanine dichloro tin, phthalocyanine oxygen tin, perfluoro CuPc, perfluoro Phthalocyanine Zinc and the perfluoro phthalocyanine cobalt; Described second organic semiconductor layer (4) is metal-free phthalocyanine or containing metal phthalocyanine and functionalized variant thereof; A kind of in the preferred CuPc of metallic phthalocyanine, phthalocyanine nickel, phthalocyanine cobalt, ferrous phthalocyanine, Phthalocyanine Zinc, phthalocyanine lead and the phthalocyanine tin; The functionalized variant of metallic phthalocyanine is a kind of in ranadylic phthalocyanine, TiOPc, phthalocyanine chlorine aluminium, phthalocyanine dichloro tin, phthalocyanine oxygen tin, perfluoro CuPc, perfluoro Phthalocyanine Zinc and the perfluoro phthalocyanine cobalt.
3. contain the organic semiconductor gas transducer of organic heterojunction by claim 1 or 2 described gas sensing layers, it is characterized in that the thickness of said inducing layer (2) is not less than 2 nanometers, be not more than 10 nanometers.
4. contain the organic semiconductor gas transducer of organic heterojunction by claim 1 or 2 described gas sensing layers, it is characterized in that the thickness of described first organic semiconductor layer (3) is not less than 1.5 nanometers, be not more than 20 nanometers.
5. contain the organic semiconductor gas transducer of organic heterojunction by claim 1 or 2 described gas sensing layers, it is characterized in that the thickness of described second organic semiconductor layer (4) is not less than 0.2 nanometer, be not more than 1.5 nanometers.
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