CN102692445B - 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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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 of gas sensing layer containing organic heterojunction.
Technical background
Along with the development of organic semiconductor science and technology, scientist find, a lot of organic semiconducting materials to some toxic and harmfuls, as NO
2etc. the response with very sensitivity, the sensor adopting this type of material to prepare has high sensitivity.The people such as B.Bott (B.Bott andT.A.Jones Sensors and Actuators 1984,5,43) report organic semiconducting materials phthalocyanine Pb more than 100 DEG C time, be the NO of part per billion in volume fraction
2in environment, film conductance can obviously increase.Sensors with auxiliary electrode works usually in high temperature environments, limits its range of application.Therefore the sensor that can detect under room temperature environment is developed imperative.The people such as M.Passard (M.Passard, A.Pauly, J.P.Blanc, S.Dogo, J.P.Germain, C.Maleysson, Thin Solid Films, 1994,237,272-276) research discovery, different gas molecules is due to redox characteristic difference, oxidation or reduction reaction can occur after being adsorbed by phthalocyanine thin film, and produce free hole charge carrier or electronic carrier in film, therefore film conductance is changed.The people such as T.Someya (T.Someya, H.E.Katz, A.Gelperin, A.J.Lovingerand A.Dodabalapur, Applied.Physics.Letter.2002,81,3079-3081) study and propose, the absorption position of organic gas-sensitive film and gas is mainly at grain boundaries, and the polycrystal film therefore with relatively large specific surface area is widely studied always.But surface of polycrystalline membrane anisotropy is serious, the activation energy wider distribution of gas absorption-desorption process needs of film surface active site, desorption speed is affected seriously by active site at a slow speed.The polycrystalline film that these specific surface areas are larger realizes often through thick film (0.5-1 micron), and under room temperature, the diffusion of gas in thin-film body can significant prolongation sensor response time and turnaround time.Ultrathin membrane can realize room temperature and respond fast, and VOPc ultrathin membrane can detect 100,000/NO under room temperature
2and obviously increase in high concentrations of gas sensitivity.The distribution of ultrathin membrane surface potential is relatively uniform concentrates, and crystal boundary number is less, and under room temperature, less than 5/1000000ths light concentration gas sensitivity are not high.Therefore, regulating the redox-potential on organic semiconductor thin-film surface to make it more easily and between sensitive gas, Charger transfer occurs is the effective means improving organic semiconductor gas transducer performance.2005, the people such as Wang Jun (J.Wang, H.B.Wang, X.J.Yan, H.C.Hang, D.H.Yan, AppliedPhysics Letters, 2005,87,093507) reported two kinds of organic semiconductor interface accumulation free carriers, formed heterojunction.The accumulation of free carrier causes heterojunction boundary place to there is higher conductance, causes the position of two kinds, heterojunction boundary place organic semi-conductor conduction band and valence band to change simultaneously.Namely can be changed the redox-potential of material by the Heterojunction Effect between organic semiconductor, thus improve the susceptibility of material for gaseous.The 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, in the organic heterojunction adopting weak epitaxial growth method to prepare, the change of this redox-potential caused by Heterojunction Effect can go deep into the region of 40 nanometers near heterojunction boundary.
Summary of the invention
The object of this invention is to provide the organic semiconductor gas transducer of gas sensing layer containing organic heterojunction.
Principle of the present invention utilizes between two kinds of organic semiconducting materials Charger transfer formation heterojunction occurs, and changes the redox-potential of film surface, thus improve sensor to the response of sensitive gas.
Gas sensing layer provided by the invention comprises the first gas sensing layer containing the organic semiconductor gas transducer of organic heterojunction and the second gas sensing layer organic semiconductor gas transducer containing organic heterojunction containing the organic semiconductor gas transducer of organic heterojunction.
Fig. 1 is the structural representation that the first gas sensing layer that the present invention relates to contains the organic semiconductor gas transducer of organic heterojunction.
(A) the first gas sensing layer of the present invention contains being constructed as follows of the organic semiconductor gas transducer of organic heterojunction: substrate 1, inducing layer 2, first organic semiconductor layer 3, second organic semiconductor layer 4 connect in turn, the film of the second organic semiconductor layer 4 is discontinuous film, and after metal electrode 5 part covers the second organic semiconductor layer 4, the have part corresponding with the first organic semiconductor layer 3 connects; Weak epitaxial relationship is there is between described inducing layer 2 and the first organic semiconductor layer 3, described weak epitaxial relationship is the acting force between the material molecule of inducing layer 2 and the material molecule of the first organic semiconductor layer 3 is Van der Waals force, and there is epitaxial relationship between two kinds of molecular crystal lattices; Heterojunction is formed due to Charger transfer between the first described organic semiconductor layer 3 and the second organic semiconductor layer 4 material;
Described substrate 1 is insulating material, and it is glass or pottery, or covers the compound substance of one deck insulating material formation at conductive material surface, and it is the heavily doped silicon chip forming layer of silicon dioxide in surface heat growth; If the r.m.s. roughness of substrate surface (RMS) is greater than 1 nanometer, needs insulation polymer coating as polymethylmethacrylate (PMMA) or polyvinyl alcohol (PVA) (PVA) smoothing;
Described inducing layer 2 is six biphenyl (p-6P), 2,7-bis-(4-xenyl)-Fei (BPPh), 2,5-bis-(4-1,1 ': 4 ', 1 "-terphenyl)-thiophene (3PT) and 2; one in 7-bis-(4-4 '-fluorodiphenyl base)-Fei (F2-BPPh), thickness is not less than 2 nanometers, is not more than 10 nanometers;
Described first organic semiconductor layer 3 is metal-free phthalocyanine (H
2or containing metal phthalocyanine and functionalized variant thereof Pc); Metallic phthalocyanine is the one in CuPc (CuPc), Nickel Phthalocyanine (NiPc), Cobalt Phthalocyanine (CoPc), ferrous phthalocyanine (FePc), Phthalocyanine Zinc (ZnPc), phthalocyanine Pb (PbPc) and Tin Phthalocyanine (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
16and perfluoro Cobalt Phthalocyanine (F ZnPc)
16coPc) one in; Its thickness is not less than 1.5 nanometers, is not more than 20 nanometers;
The second described organic semiconductor layer 4 is metal-free phthalocyanine (H
2or containing metal phthalocyanine and functionalized variant thereof Pc); Metallic phthalocyanine is the one in CuPc (CuPc), Nickel Phthalocyanine (NiPc), Cobalt Phthalocyanine (CoPc), ferrous phthalocyanine (FePc), Phthalocyanine Zinc (ZnPc), phthalocyanine Pb (PbPc) and Tin Phthalocyanine (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
16and perfluoro Cobalt Phthalocyanine (F ZnPc)
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 gold.
Fig. 2 is the structural representation that the second gas sensing layer that the present invention relates to contains the organic semiconductor gas transducer of organic heterojunction.
(B) the second gas sensing layer of the present invention contains being constructed as follows of the organic semiconductor gas transducer of organic heterojunction: substrate 1, inducing layer 2, first organic semiconductor layer 3 connect in turn, first organic semiconductor layer 3 is all connected with the second organic semiconductor layer 4, metal electrode 5, and metal electrode 5 and the first organic semiconductor layer 3 also have part directly to contact; Weak epitaxial relationship is there is between described inducing layer 2 and the first organic semiconductor layer 3; Heterojunction is formed because of Charger transfer between described organic semiconductor layer 3 and organic semiconductor layer 4; The film of the 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).
Gas sensing layer involved in the present invention can adopt the mode of planar diode to measure containing the organic semiconductor gas transducer of organic heterojunction, measures by the positive and negative electrode of metal electrode 5 respectively as diode.For substrate be conductive material surface cover one deck insulating material formed compound substance, the mode of transistor can also be adopted to measure, by the gate electrode of conductive material as transistor, measure using electrode 5 as the source/drain electrode of transistor.
Gas sensing layer of the present invention is as follows containing the preparation method of the organic semiconductor gas transducer of organic heterojunction:
(I) the first gas sensing layer that the present invention relates to is as follows containing the organic semiconductor gas transducer method for making of organic heterojunction:
(1) substrate 1 is insulating material, and it is glass or pottery, or covers the compound substance of one deck insulating material formation at conductive material surface, and it is the heavily doped silicon chip forming layer of silicon dioxide in surface heat growth; If the r.m.s. roughness of substrate surface (RMS) is greater than 1 nanometer, needs insulation polymer coating as polymethylmethacrylate (PMMA) or polyvinyl alcohol (PVA) (PVA) smoothing;
(2) at substrate 1 surface vacuum deposition inducing layer 2, thickness is not less than 2 nanometers, be no more than 10 nanometers, material is six biphenyl (p-6P), 2,7-bis-(4-xenyl)-Fei (BPPh), 2,5-bis-(4-1,1 ': 4 ', 1 "-terphenyl) one in-thiophene (3PT) and 2,7-bis-(4-4 '-fluorodiphenyl base)-Fei (F2-BPPh);
(3) deposit the first organic semi-conductive layer 3 at inducing layer 2 surface vacuum, thickness is not less than 1.5 nanometers, is not more than 20 nanometers; Weak epitaxial relationship is there is between described inducing layer 2 and the first organic semiconductor layer 3, described weak epitaxial relationship is the acting force between the material molecule of inducing layer 2 and the material molecule of organic semiconductor layer 3 is Van der Waals force, and there is epitaxial relationship between two kinds of molecular crystal lattices; The material of the first organic semi-conductive layer 3 is metal-free phthalocyanine (H
2or containing metal phthalocyanine and functionalized variant thereof Pc); Metallic phthalocyanine is the one in CuPc (CuPc), Nickel Phthalocyanine (NiPc), Cobalt Phthalocyanine (CoPc), ferrous phthalocyanine (FePc), Phthalocyanine Zinc (ZnPc), phthalocyanine Pb (PbPc) and Tin Phthalocyanine (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
16and perfluoro Cobalt Phthalocyanine (F ZnPc)
16coPc) one in;
(4) film depositing the second organic semiconductor layer 4, second organic semiconductor layer 4 at the first organic semiconductor layer 3 surface vacuum is discontinuous film; Because Charger transfer forms heterojunction between the second described organic semiconductor layer 4 and the first organic semiconductor layer 3 material; The thickness of the second described 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
2or containing metal phthalocyanine and functionalized variant thereof Pc); Metallic phthalocyanine is the one in CuPc (CuPc), Nickel Phthalocyanine (NiPc), Cobalt Phthalocyanine (CoPc), ferrous phthalocyanine (FePc), Phthalocyanine Zinc (ZnPc), phthalocyanine Pb (PbPc) and Tin Phthalocyanine (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
16and perfluoro Cobalt Phthalocyanine (F ZnPc)
16coPc) one in;
(5) bushing vacuum deposited metal electrode 5 is utilized at the second organic semiconductor layer 4 part surface;
Wherein, background vacuum is not less than 8.0 × 10
-4pa, metal electrode rate of sedimentation is 20 nm/minute, and the rate of sedimentation of other materials is 1 nm/minute.
The thickness of organic semiconductor layer is determined by the product of rate of sedimentation and sedimentation time, and when the two product is less than characteristic thickness, gained film is discontinuous film; The thickness of the characteristic that the material that the second described organic semiconductor layer 4 uses is formed all is greater than 1.5 nanometers, and the film of the second organic semiconductor layer 4 therefore prepared as stated above is discontinuous film.
(II) the second gas sensing layer that the present invention relates to is as follows containing the organic semiconductor gas transducer method for making of organic heterojunction:
(1) substrate 1 is insulating material, and it is glass or pottery, or covers the compound substance of one deck insulating material formation at conductive material surface, and it is form layer of silicon dioxide in the growth of heavily doped silicon chip surface heat; If the r.m.s. roughness of substrate surface (RMS) is greater than 1 nanometer, the polymer coating of needs insulation is as smoothing in polymethylmethacrylate (PMMA) or polyvinyl alcohol (PVA) (PVA) etc.;
(2) at substrate surface vacuum moulding machine inducing layer 2, thickness is not less than 2 nanometers, be no more than 10 nanometers, material is six biphenyl (p-6P), 2,7-bis-(4-xenyl)-Fei (BPPh), 2,5-bis-(4-1,1 ': 4 ', 1 "-terphenyl) one in-thiophene (3PT) and 2,7-bis-(4-4 '-fluorodiphenyl base)-Fei (F2-BPPh);
(3) the first organic semi-conductive layer 3 is deposited at inducing layer 2 surface vacuum, weak epitaxial relationship is there is between described inducing layer 2 and the first organic semiconductor layer 3, thickness is not less than 1.5 nanometers, be not more than 20 nanometers, described weak epitaxial relationship is the acting force between the material molecule of inducing layer 2 and the material molecule of the first organic semiconductor layer 3 is Van der Waals force, and there is epitaxial relationship between two kinds of molecular crystal lattices; The material of the first organic semi-conductive layer 3 is metal-free phthalocyanine (H
2or containing metal phthalocyanine and functionalized variant thereof Pc); Metallic phthalocyanine is the one in CuPc (CuPc), Nickel Phthalocyanine (NiPc), Cobalt Phthalocyanine (CoPc), ferrous phthalocyanine (FePc), Phthalocyanine Zinc (ZnPc), phthalocyanine Pb (PbPc) and Tin Phthalocyanine (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
16and perfluoro Cobalt Phthalocyanine (F ZnPc)
16coPc) one in;
(4) bushing vacuum deposited metal electrode 5 is utilized at the part surface of the first organic semiconductor layer 3;
(5) film that the partial vacuum beyond the empty deposit metal electrodes 5 in the surface of the first organic semiconductor layer 3 deposits the second organic semiconductor layer 4, second organic semiconductor layer 4 is discontinuous film; Because Charger transfer forms heterojunction between the second described organic semiconductor layer 4 and the first organic semiconductor layer 3 material; The thickness of the second described organic semiconductor layer 4 is not less than 0.2 nanometer, is not more than 1.5 nanometers, and the material of the second organic semiconductor layer 4 is metal-free phthalocyanine (H2Pc) or containing metal phthalocyanine and functionalized variant thereof; Metallic phthalocyanine is the one in CuPc (CuPc), Nickel Phthalocyanine (NiPc), Cobalt Phthalocyanine (CoPc), ferrous phthalocyanine (FePc), Phthalocyanine Zinc (ZnPc), phthalocyanine Pb (PbPc) and Tin Phthalocyanine (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
16and perfluoro Cobalt Phthalocyanine (F ZnPc)
16coPc) one in;
Wherein, background vacuum is not less than 8.0 × 10
-4pa, metal electrode rate of sedimentation is 20 nm/minute, and the rate of sedimentation of other materials is 1 nm/minute.
The thickness of organic semiconductor layer is determined by the product of rate of sedimentation and sedimentation time, and when the two product is less than characteristic thickness, gained film is discontinuous film.The thickness of the characteristic that the material that the second described organic semiconductor layer 4 uses is formed all is greater than 1.5 nanometers, and the film of the second organic semiconductor layer 4 therefore prepared as stated above is discontinuous film.Because metal electrode deposits prior to the second organic semiconductor layer 4, have part second organic semiconductor 4 when therefore depositing the second organic semiconductor layer 4 and be deposited on surface of metal electrode, the impact of this point on device is negligible.
Beneficial effect: gas sensing layer provided by the invention, containing the organic semiconductor gas transducer of organic heterojunction, comprises the first gas sensing layer containing the organic semiconductor gas transducer device of organic heterojunction and the second gas sensing layer organic semiconductor gas transducer containing organic heterojunction.Gas sensing layer provided by the invention is utilize between two kinds of organic semiconducting materials Charger transfer formation heterojunction occurs containing the organic semiconductor gas transducer of organic heterojunction, change the redox-potential of film surface, thus improve sensor to the response of sensitive gas.Gas sensing layer provided by the invention is high containing susceptibility under the organic semiconductor gas transducer room temperature condition of organic heterojunction, gas sensing layer thickness is little, effectively shorten the response/turnaround time of device, and utilize the disposable preparation completing device of vacuum deposition method, do not need the subsequent techniques such as annealing, simplify the preparation process of device.Gas sensing layer provided by the invention can detect containing the organic semiconductor gas transducer of organic heterojunction the NO that volume fraction is 5/1000000ths
2gas, and respond/reply and all can complete in 10 minutes.
Accompanying drawing explanation
Fig. 1 is the structural representation that the first gas sensing layer that the present invention relates to contains the organic semiconductor gas transducer of organic heterojunction.
Fig. 2 is the structural representation that the second gas sensing layer that the present invention relates to contains the organic semiconductor gas transducer of organic heterojunction.
Fig. 3 be the gas sensing layer that adopts the present invention of configuration shown in Fig. 1 to relate to containing under the organic semiconductor gas transducer room temperature of organic heterojunction at the response/return curve to volume fraction being millionth NO2 gas.Wherein, substrate is that Film by Thermal Oxidation forms SiO
2heavily doped silicon chip, inducing layer is p-6P, thickness 4 nanometer, and organic semiconductor layer 3 is TiOPc, and thickness 3 nanometer, machine semiconductor layer 4 is F
16cuPc, thickness 0.5 nanometer, adopts gold as electrode.
Fig. 4 is the second gas sensing layer of adopting the present invention of configuration shown in Fig. 2 to relate to containing being the NO of 5/1000000ths to volume fraction under the organic semiconductor gas transducer room temperature of organic heterojunction
2response/the return curve of gas.Wherein, substrate is the SiO of surface coverage one deck heat growth
2heavily doped silicon chip, inducing layer is p-6P, thickness 2 nanometer, and organic semiconductor layer 3 is VOPc, thickness 2 nanometer, and organic semiconductor layer 4 is CuPc, thickness 1 nanometer, adopt gold as electrode.
Embodiment
Metal-free phthalocyanine (H is adopted below in all embodiments
2pc), CuPc (CuPc), Nickel Phthalocyanine (NiPc), Cobalt Phthalocyanine (CoPc), ferrous phthalocyanine (FePc), Phthalocyanine Zinc (ZnPc), phthalocyanine Pb (PbPc), Tin Phthalocyanine (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 Cobalt Phthalocyanine (F
16coPc), 2,7-bis-(4-xenyl)-Fei (BPPh), 2,5-bis-(4-1,1 ': 4 ', 1 "-terphenyl)-thiophene (3PT); 2,7-bis-(4-4 '-fluorodiphenyl base)-Fei (F2-BPPh) is commercial product, uses after purchase after vacuum sublimation purification secondary.Glass, pottery, Film by Thermal Oxidation forms silicon dioxide (SiO
2) heavily doped silicon chip, cleaning after use, polymethyl-benzene e pioic acid methyl ester (PMMA), polyvinyl alcohol (PVA) (PVA) is commercially produced product, buy after directly use.
Embodiment 1
The first gas sensing layer of the present invention contains the configuration of the organic semiconductor gas transducer of organic heterojunction as shown in Figure 1, and concrete preparation method is as follows:
(1) substrate 1 is insulating material, and it is glass or pottery, or covers the compound substance of one deck insulating material formation at conductive material surface, and it is the heavily doped silicon chip forming layer of silicon dioxide in surface heat growth; If the r.m.s. roughness of substrate surface (RMS) is greater than 1 nanometer, needs insulation polymer coating as polymethylmethacrylate (PMMA) or polyvinyl alcohol (PVA) (PVA) smoothing;
(2) at substrate 1 surface vacuum deposition inducing layer 2, thickness is not less than 2 nanometers, be no more than 10 nanometers, material is six biphenyl (p-6P), 2,7-bis-(4-xenyl)-Fei (BPPh), 2,5-bis-(4-1,1 ': 4 ', 1 "-terphenyl) a kind of in-thiophene (3PT) and 2,7-bis-(4-4 '-fluorodiphenyl base)-Fei (F2-BPPh);
(3) deposit the first organic semi-conductive layer 3 at inducing layer 2 surface vacuum, between described inducing layer 2 and the first organic semiconductor layer 3, there is weak epitaxial relationship; Described weak epitaxial relationship is the acting force between the material molecule of inducing layer 2 and the material molecule of organic semiconductor layer 3 is Van der Waals force, and there is 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 the first organic semi-conductive layer 3 is metal-free phthalocyanine (H
2or containing metal phthalocyanine and functionalized variant thereof Pc); Metallic phthalocyanine is the one in CuPc (CuPc), Nickel Phthalocyanine (NiPc), Cobalt Phthalocyanine (CoPc), ferrous phthalocyanine (FePc), Phthalocyanine Zinc (ZnPc), phthalocyanine Pb (PbPc) and Tin Phthalocyanine (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
16and perfluoro Cobalt Phthalocyanine (F ZnPc)
16coPc) a kind of in;
(4) film depositing the second organic semiconductor layer 4, second organic semiconductor layer 4 at the first organic semiconductor layer 3 surface vacuum is discontinuous film; Because Charger transfer forms heterojunction between the second described organic semiconductor layer 4 and the first organic semiconductor layer 3 material; The thickness of the second described organic semiconductor layer 4 is not less than 0.2 nanometer, is not more than 1.5 nanometers, and the material of the second organic semiconductor layer 4 is metal-free phthalocyanine (H
2or containing metal phthalocyanine and functionalized variant thereof Pc); Metallic phthalocyanine is the one in CuPc (CuPc), Nickel Phthalocyanine (NiPc), Cobalt Phthalocyanine (CoPc), ferrous phthalocyanine (FePc), Phthalocyanine Zinc (ZnPc), phthalocyanine Pb (PbPc) and Tin Phthalocyanine (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
16and perfluoro Cobalt Phthalocyanine (F ZnPc)
16coPc) a kind of in;
(5) bushing vacuum deposited metal electrode 5 is utilized at the second organic semiconductor layer 4 part surface; The material of metal electrode 5 is gold;
Wherein, background vacuum is not less than 8.0 × 10
-4pa, metal electrode rate of sedimentation is 20 nm/minute, and the rate of sedimentation of other materials is 1 nm/minute.
The thickness of organic semiconductor layer is determined by the product of rate of sedimentation and sedimentation time, and when the two product is less than characteristic thickness, gained film is discontinuous film; The thickness of the characteristic that the material that the second described organic semiconductor layer 4 uses is formed all is greater than 1.5 nanometers, and the film of the second organic semiconductor layer 4 therefore prepared as stated above is discontinuous film.
Fig. 3 is the first gas sensing layer of adopting the present invention of configuration shown in Fig. 1 to relate to containing being millionth NO to volume fraction under the organic semiconductor gas transducer room temperature of organic heterojunction
2response/the return curve of gas.Wherein, substrate is that Film by Thermal Oxidation forms SiO
2heavily doped silicon chip, inducing layer is p-6P, thickness 4 nanometer, and organic semiconductor layer 3 is TiOPc, and thickness 3 nanometer, machine semiconductor layer 4 is F
16cuPc, thickness 0.5 nanometer, adopts gold as electrode.Compare with reference device, reference device does not respond, and the sensitivity adopting the first organic semiconductor gas transducer of structure shown in Fig. 1 is 17,2.5 minutes response times, 7 minutes turnaround times.The described response time be from logical NO2 start to reach peak value 50% required time to the current value of sensor, turnaround time stops logical NO2 to start to reduce to time needed for peak value 50% to the current value of sensor.Therefore, the organic semiconductor gas transducer adopting gas sensing layer of the present invention to contain organic heterojunction effectively can improve the sensitivity of device, shortens the response/turnaround time of device.
Table 1 give adopt above-mentioned technique and the first gas sensing layer prepared by the specified criteria of table 1 containing the composition of the organic semiconductor gas transducer of organic heterojunction and at NO
2device parameters when volume fraction is 5/1000000ths.
Table 1
Note: SiO
2refer to that Film by Thermal Oxidation forms SiO
2heavily doped silicon chip, sensitivity and mark after response/turnaround time No. * be the data adopting transistor metering system to obtain, what all the other did not do to mark is the data adopting planar diode metering system to obtain.
Embodiment 2
The organic semiconductor gas transducer method for making that the second gas sensing layer that the present invention of structure relates to as shown in Figure 2 contains organic heterojunction is as follows:
(1) substrate 1 is insulating material, and it is glass or pottery, or covers the compound substance of one deck insulating material formation at conductive material surface, and it is form layer of silicon dioxide in the growth of heavily doped silicon chip surface heat; If the r.m.s. roughness of substrate surface (RMS) is greater than 1 nanometer, needs insulation polymer coating as polymethylmethacrylate (PMMA) or polyvinyl alcohol (PVA) (PVA) smoothing;
(2) at substrate surface vacuum moulding machine inducing layer 2, thickness is not less than 2 nanometers, be no more than 10 nanometers, material is six biphenyl (p-6P), 2,7-bis-(4-xenyl)-Fei (BPPh), 2,5-bis-(4-1,1 ': 4 ', 1 "-terphenyl) one in-thiophene (3PT) and 2,7-bis-(4-4 '-fluorodiphenyl base)-Fei (F2-BPPh);
(3) the first organic semi-conductive layer 3 is deposited at inducing layer 2 surface vacuum, weak epitaxial relationship is there is between described inducing layer 2 and the first organic semiconductor layer 3, described weak epitaxial relationship is the acting force between the material molecule of inducing layer 2 and the material molecule of the first organic semiconductor layer 3 is Van der Waals force, and there is epitaxial relationship between two kinds of molecular crystal lattices; The thickness of the first organic semi-conductive layer 3 is not less than 1.5 nanometers, is not more than 20 nanometers, and material is metal-free phthalocyanine (H
2or containing metal phthalocyanine and functionalized variant thereof Pc); Metallic phthalocyanine is the one in CuPc (CuPc), Nickel Phthalocyanine (NiPc), Cobalt Phthalocyanine (CoPc), ferrous phthalocyanine (FePc), Phthalocyanine Zinc (ZnPc), phthalocyanine Pb (PbPc) and Tin Phthalocyanine (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
16and perfluoro Cobalt Phthalocyanine (F ZnPc)
16coPc) one in;
(4) bushing vacuum deposited metal electrode 5 is utilized at the first organic semiconductor layer 3 part surface; The material of metal electrode 5 is gold;
(5) film that the partial vacuum beyond the empty deposit metal electrodes 5 in the surface of the first organic semiconductor layer 3 deposits the second organic semiconductor layer 4, second organic semiconductor layer 4 is discontinuous film; Because Charger transfer forms heterojunction between the second described organic semiconductor layer 4 and the first organic semiconductor layer 3 material, the thickness of the second described 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
2or containing metal phthalocyanine and functionalized variant thereof Pc); Metallic phthalocyanine is the one in CuPc (CuPc), Nickel Phthalocyanine (NiPc), Cobalt Phthalocyanine (CoPc), ferrous phthalocyanine (FePc), Phthalocyanine Zinc (ZnPc), phthalocyanine Pb (PbPc) and Tin Phthalocyanine (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
16and perfluoro Cobalt Phthalocyanine (F ZnPc)
16coPc) one in;
Wherein, background vacuum is not less than 8.0 × 10
-4pa, metal electrode rate of sedimentation is 20 nm/minute, and the rate of sedimentation of other materials is 1 nm/minute.
The thickness of organic semiconductor layer is determined by the product of rate of sedimentation and sedimentation time, and when the two product is less than characteristic thickness, gained film is discontinuous film.The thickness of the characteristic that the material that the second described organic semiconductor layer 4 uses is formed all is greater than 1.5 nanometers, and the film of the second organic semiconductor layer 4 therefore prepared as stated above is discontinuous film.Because metal electrode deposits prior to the second organic semiconductor layer 4, have part second organic semiconductor 4 when therefore depositing the second organic semiconductor layer 4 and be deposited on surface of metal electrode, the impact of this point on device is negligible.
Fig. 4 provides the organic semiconductor gas transducer response/return curve when nitrogen dioxide volume fraction be 5/1000000ths of gas sensing layer containing organic heterojunction of structure shown in Fig. 2.Wherein, substrate is the SiO of surface coverage one deck heat growth
2heavily doped silicon chip, inducing layer is p-6P, thickness 2 nanometer, and organic semiconductor layer 3 is VOPc, thickness 2 nanometer, and organic semiconductor layer 4 is CuPc, thickness 1 nanometer, adopt gold as electrode.Compare with reference device, reference device, without response, adopts gas sensing layer provided by the invention to be 10 containing the organic semiconductor gas transducer sensitivity of organic heterojunction, 2.5 minutes response times, 7 minutes turnaround times.The described response time be from logical NO2 start to reach peak value 50% required time to the current value of sensor, turnaround time stops logical NO2 to start to reduce to time needed for peak value 50% to the current value of sensor.Therefore, the organic semiconductor gas transducer adopting gas sensing layer of the present invention to contain organic heterojunction effectively can improve the sensitivity of device, reduces the response/turnaround time of device.
Table 2 give adopt above-mentioned technique and the second gas sensing layer prepared by the specified criteria of table 2 containing the composition of the organic semiconductor gas transducer of organic heterojunction and at NO
2device parameters when volume fraction is 5/1000000ths.
Table 2
Note: SiO
2refer to that Film by Thermal Oxidation forms silicon dioxide (SiO
2) heavily doped silicon chip, sensitivity and mark after response/turnaround time No. * be the data adopting transistor metering system to obtain, what all the other did not do to mark is the data adopting planar diode metering system to obtain.
Claims (5)
1. gas sensing layer is containing the organic semiconductor gas transducer of organic heterojunction, it is characterized in that, comprises the first gas sensing layer containing the organic semiconductor gas transducer of organic heterojunction and the second gas sensing layer organic semiconductor gas transducer containing organic heterojunction; (A) the first gas sensing layer contains being constructed as follows of the organic semiconductor gas transducer of organic heterojunction: substrate (1), inducing layer (2), the first organic semiconductor layer (3), the second organic semiconductor layer (4) connect in turn, the film of the second organic semiconductor layer (4) is discontinuous film, and the part that has that metal electrode (5) part covers the second organic semiconductor layer (4) corresponding with the first organic semiconductor layer (3) afterwards connects; Weak epitaxial relationship is there is between described inducing layer (2) and the first organic semiconductor layer (3), described weak epitaxial relationship is the acting force between the material molecule of inducing layer (2) and the material molecule of the first organic semiconductor layer (3) is Van der Waals force, and there is epitaxial relationship between two kinds of molecular crystal lattices; Heterojunction is formed due to Charger transfer between described the first organic semiconductor layer (3) and the second organic semiconductor layer (4); (B) the second gas sensing layer contains being constructed as follows of the organic semiconductor gas transducer of organic heterojunction: substrate (1), inducing layer (2), the first organic semiconductor layer (3) connect in turn, first organic semiconductor layer (3) is all connected with the second organic semiconductor layer (4), metal electrode (5), and metal electrode (5) and the first organic semiconductor layer (3) also have part directly to contact; Weak epitaxial relationship is there is between described inducing layer (2) and the first organic semiconductor layer (3); Heterojunction is formed because of Charger transfer between described the first organic semiconductor layer (3) and the second organic semiconductor layer (4); The film of the second organic semiconductor layer (4) is discontinuous film.
2. by the organic semiconductor gas transducer of gas sensing layer according to claim 1 containing organic heterojunction, it is characterized in that, described substrate (1) is insulating material, it is glass or pottery, or the compound substance of one deck insulating material formation is covered at conductive material surface, it is the heavily doped silicon chip forming layer of silicon dioxide in surface heat growth; If the r.m.s. roughness of substrate surface is greater than 1 nanometer, the polymer coating of needs insulation is smoothing, and the polymer coating of described insulation is polymethylmethacrylate or polyvinyl alcohol (PVA); Described inducing layer (2) is six biphenyl, 2,7-bis-(4 one xenyl)-Fei, 2,5-bis-(4-1,1':4', 1 〞-terphenyl)-thiophene) and 2,7-bis-(4-4 ˊ-fluorodiphenyl base)-Fei in one; Described the first organic semiconductor layer (3) is metal-free phthalocyanine or containing metal phthalocyanine and functionalized variant thereof; Metallic phthalocyanine is the one in CuPc, Nickel Phthalocyanine, Cobalt Phthalocyanine, ferrous phthalocyanine, Phthalocyanine Zinc, phthalocyanine Pb and Tin Phthalocyanine; The functionalized variant of metallic phthalocyanine is the one in ranadylic phthalocyanine, TiOPc, phthalocyanine chlorine aluminium, phthalocyanine dichloro tin, phthalocyanine oxygen tin, perfluoro CuPc, perfluoro Phthalocyanine Zinc and perfluoro Cobalt Phthalocyanine; Described the second organic semiconductor layer (4) is metal-free phthalocyanine or containing metal phthalocyanine and functionalized variant thereof; Metallic phthalocyanine is the one in CuPc, Nickel Phthalocyanine, Cobalt Phthalocyanine, ferrous phthalocyanine, Phthalocyanine Zinc, phthalocyanine Pb and Tin Phthalocyanine; The functionalized variant of metallic phthalocyanine is the one in ranadylic phthalocyanine, TiOPc, phthalocyanine chlorine aluminium, phthalocyanine dichloro tin, phthalocyanine oxygen tin, perfluoro CuPc, perfluoro Phthalocyanine Zinc and perfluoro Cobalt Phthalocyanine.
3., by the organic semiconductor gas transducer of the gas sensing layer described in claim 1 or 2 containing organic heterojunction, it is characterized in that the thickness of described inducing layer (2) is not less than 2 nanometers, be not more than 10 nanometers.
4., by the organic semiconductor gas transducer of the gas sensing layer described in claim 1 or 2 containing organic heterojunction, it is characterized in that the thickness of described the first organic semiconductor layer (3) is not less than 1.5 nanometers, be not more than 20 nanometers.
5., by the organic semiconductor gas transducer of the gas sensing layer described in claim 1 or 2 containing organic heterojunction, it is characterized in that the thickness of described the second organic semiconductor layer (4) is not less than 0.2 nanometer, be not more than 1.5 nanometers.
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| EP3325958A4 (en) * | 2015-07-10 | 2019-01-23 | Robert Bosch GmbH | Sensor element for a chemical sensor and chemical sensor |
| CN107561129B (en) * | 2017-07-04 | 2020-02-18 | 上海工程技术大学 | Heterojunction gas sensor with inorganic-organic composite structure |
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