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    • 专利摘要:
    A method of obtaining an organic N-type semiconductor by means of uv-vis irradiation. The invention relates to a process for obtaining an organic N-type semiconductor by irradiating an organic p-type semiconductor with uv-vis radiation. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2613546A1
    申请号:ES201531706
    申请日:2015-11-24
    公开日:2017-05-24
    发明作者:Mariano Campoy Quiles；Alejandro Rodolfo GOÑI TASADA；Bernhard DÖRLING；Christian Müller；Jason Ryan
    申请人:Consejo Superior de Investigaciones Cientificas CSIC；
    IPC主号:
    专利说明:

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    A procedure for obtaining an organic semiconductor type n by
    UV-VIS irradiation
    DESCRIPTION
    The invention relates to a method of obtaining an organic semiconductor of type n by irradiating an organic semiconductor of type p with UV-VIS radiation.
    STATE OF THE TECHNIQUE
    A wide range of organic electronic applications depend on the availability of organic semiconductors of both p and n type, and the possibility of depositing them in the form of sequential layers or other spatial arrangements. Examples include diode transport layers (OLED, photovoltaic, etc.), transistor technology, which forms the basis of complementary logic and circuit systems, as well as the p and n branches of a thermoelectric generator. Normally, a judicious selection of orthogonal solvents combined with additive modeling techniques during deposition, such as inkjet printing, is used to form the p and n regions in devices processed from a solution. If a higher resolution is required (below ~ 100 ^ .m), then multiple stages of lithographic procedures are mandatory.
    Apart from inkjet printing, organic thermoelectric generators are prepared using various procedures, including drip deposit, spray coating or filtration (in vacuo) of the solution, to obtain individual layers, and then assemble the entire device . In all these cases, the type n character is obtained by molecular doping of the organic semiconductor, or by forming compounds with n-type filler material, such as carbon nanotubes doped with nitrogen.
    In addition, organic n-type materials in particular are difficult to handle, due to their inherent chemical instability by oxidation in the air, since their LUMO is normally located approximately 3 eV below the vacuum level. To circumvent this, various strategies have been employed, such as doping with stable intermediate compounds in
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    air or through efforts to synthesize compounds with a precisely controlled LUMO level.
    DESCRIPTION OF THE INVENTION
    It can be discovered in the state of the art that the manufacturing processes of semiconductor devices of type n or p usually require the deposit of both types of materials, of type both n and p. In the present invention only a solution of a p-type material has to be deposited and subsequently irradiated with light. Therefore, the present invention significantly simplifies the manufacturing process of said class of devices.
    Because the tank itself comprises only a single stage, this automatically guarantees good electrical and physical contact between regions n and p, thereby minimizing contact resistance and avoiding wetting and delamination problems. All this makes it possible to reduce the minimum complexity of the process, not only by renouncing the deposit stage for the complementary semiconductor layer, but also potentially avoiding the need for additional deposit stages of metallic interconnection layers in some devices such as thermoelectric generators.
    When complex multilayer structures are deposited from a solution, a careful selection of orthogonal solvents is necessary, so as not to damage any of the exposed underlying layers. Being able to prepare a similar structure with fewer deposit stages immediately relaxes the requirements, or if desired, instead allows the manufacture of even more complex structures at no additional cost.
    The procedure also helps to obtain a greater homogeneity of thickness compared to the sequential additive manufacturing.
    Because the delineation is done with light, the resolution of the pyn regions can be improved from approximately 50 p, m, resolution characteristic of inkjet printing of the state of the art, up to only 1 p, m achievable with a standard photolithographic stage.
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    Unlike the predominant n-type organic materials, which often cannot be processed or handled in normal atmospheric conditions, the materials related to this invention are stable in air for weeks and months, as demonstrated by preparing, handling and storing them in a normal atmosphere. .
    A first aspect of the present invention relates to a method of obtaining an organic semiconductor of type n, characterized in that the process comprises the following steps:
    a) preparing a film of a p-type organic semiconductor on a substrate; wherein said p-type organic semiconductor comprises
    • a n-type semiconductor nanostructure that varies in a weight percentage between 0.1% and 60%, preferably a weight percentage between 20% and 40%; Y
    • a p-type semiconductor conjugate molecule;
    and wherein said n-type semiconductor nanostructure is dispersed in the p-type semiconductor conjugate molecule; Y
    b) irradiate the film obtained in step (a) by UV-VIS radiation with a power between 1 mW / cm2 and 100 mW / cm2 and an exposure time between 0.1 s and 600 s, preferably with a power between 40 mW / cm2 and 60 mW / cm2 and an exposure time between 50 s and 100 s.
    The process of the invention begins with the preparation of a film of a p-type organic semiconductor comprising
    • a n-type semiconductor nanostructure that varies by weight percentage between 0.1% and 60%; preferably a weight percentage between 20% and 40%; Y
    • a p-type semiconductor conjugate molecule;
    and in which the n-type semiconductor nanostructure is dispersed in the p-type semiconductor conjugate molecule;
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    In semiconductors, electric conduction is explained in terms of majority and minority carriers of electric charge. In semiconductor materials of type n, electrons are the major carriers and the holes, that is, the vacancies left by electrons, are minority carriers. In p-type semiconductor materials, the opposite is true: the holes are the major carriers and the electrons are the minor carriers. The type of carrier can be determined experimentally using, for example, the Seebeck effect or the Hall effect.
    In the present invention, the terms "organic semiconductor of type n and organic semiconductor of type p" are used inclusive, and refer to a semiconductor of type n and an organic semiconductor of type p, respectively, which comprise at least one organic component . This does not mean excluding additional inorganic components.
    The expression "semiconductor nanostructure of type n" refers herein to a material that is at least one dimension below a length of 100 nm, for example nano-scale particles, wires, bars, tubes, fibers, tapes, sheets or foils showing semiconductivity of type n.
    Preferred examples of n-type semiconductor nanostructures are carbon nanotubes doped with N, graphene sheets and graphene nanolamines doped with N, graphene nanocints doped with N, fulerenos, silicon nanowires doped with phosphorus, tellurium-based nanowires such as Bi2Te3 nanowires or PbTe nanowires), zinc oxide based nanowires, titanium oxide based nanowires, and a combination thereof.
    The term "p-type semiconductor conjugated organic molecule" refers herein to conjugated polymers or small conjugated molecules, ie organic molecules containing extended% delocalized electron systems that show p-type semiconductivity. It also includes subgroups such as polyelectrolytes and donor-acceptor polymers.
    Examples of p-type semiconductor conjugated organic molecules are polyalkylthiophenes, polyfluorenes, polyaniline (PANI), polyacetylene, polyphenylenevinylene (PPV),
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    tetracyanoquinodimethane, tetrathiafulvalene, and a combination thereof. Poly (3-hexylthiophene) (P3HT), poly (3-dodecylthiophene-2,5-diyl) (P3DDT) or poly (9,9-dioctylfluorene) are preferred.
    In the organic p-type semiconductor of the present invention, the n-type semiconductor nanostructure is dispersed in the p-type semiconductor conjugated molecule, so that the percola n-type semiconductor nanostructure through the p-type semiconductor conjugated molecule. The percolation of the n-type semiconductor nanostructure through the p-type semiconductor conjugate molecule begins for a weight percentage (concentration of percolation) of approximately 0.1%; It depends, for example, on the length of the nanotubes and the degree of aggregation. For well dispersed and very long CNT, percolation can be obtained for really low concentrations of CNT, close to 0.1%. In a preferred embodiment of the process of the invention, the n-type semiconductor nanostructure varies in a weight percentage between 20% and 40%.
    Step (a) of the process of the invention relates to the preparation of a film of a p-type organic semiconductor on a substrate.
    The substrates could be rigid or flexible.
    The substrates can consist of a glass, a ceramic, a metal, wood, a polymer such as a rubber, a mineral, concrete, a cellulosic material, a textile material such as cotton, linen, nylon, silk, velvet and leather or fabrics Biological such as skin.
    Preferred examples of substrates are flexible substrates selected from polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyimide, polyethylene (PE), polystyrene (PS), poly (vinyl chloride) (PVC), polytetrafluoroethylene (PTFE, Teflon), polypropylene (PP), polyurethane (PU), polyvinylidene fluoride (PVDF) and a combination thereof.
    In a preferred embodiment of the process of the invention, the preparation of a p-type organic semiconductor film on a substrate, that is, step (a) of the process, comprises the following steps:
    a1) add a solution of a p-type semiconductor conjugate molecule, which
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    it comprises a p-type semiconductor conjugate molecule and a solvent, to a n-type semiconductor nanostructure dispersion, comprising a n-type semiconductor nanostructure and a solvent;
    a2) stir the mixture obtained in (a1) at a temperature range between -20 ° C and 200 ° C; preferably at a temperature range between 0 ° C and 100 ° C,
    a3) deposit the solution obtained in step (a2) on a substrate.
    In step (a1), the p-type semiconductor conjugate molecule solution comprises a p-type semiconductor conjugate molecule as defined above, and a solvent. Examples of solvents are chlorobenzene, 1,2-dichlorobenzene, 1,4-dichlorobenzene, 1,2,4-trichlorobenzene, chloroform, toluene, o-xylene, p-xylene, water, methanol, ethanol and isopropanol.
    In step (a1), the n-type semiconductor nanostructure dispersion comprises a n-type semiconductor nanostructure as described above and a solvent. Examples of solvents are chlorobenzene, 1,2-dichlorobenzene, 1,4-dichlorobenzene, 1,2,4-trichlorobenzene, chloroform, toluene, o-xylene, p-xylene, water, methanol, ethanol and isopropanol.
    Step (a1) refers to the addition of a p-type semiconductor conjugate molecule solution to a n-type semiconductor nanostructure dispersion.
    Step (a2) refers to the stirring of the mixture obtained in (a1) at a temperature range between -20 ° C and 200 ° C, preferably between 0 ° C and 100 ° C. Stirring, such as sonication, is necessary to disperse n-type semiconductor nanostructures.
    Step (a3) refers to the deposit of the solution obtained in step (a3) on a substrate. Possible substrates have been defined above. Preferred deposit techniques are drip deposit, filtration, immersion coating, razor coating, die coating, spray coating, bar coating, screen printing, gravure printing, flexographic printing or printing
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    by inkjet.
    In a preferred embodiment, the process of the invention comprises a step a1 '), between step a1) and step a2), of adding a surfactant to the mixture obtained in (a1). The surfactant can help better dispersion of n-type semiconductor nanostructures.
    A wet film is obtained after stage (a3); In this preferred embodiment of the process of the invention, step (b), ie irradiation with UV-VIS radiation, is performed while the film is wet.
    Preferably, the wet film obtained in step (a) has a thickness between 10 p, m and 1000 p, m, more preferably between 100 p, m and 1000 p, m.
    In another preferred embodiment of the process of the invention, step (a) comprises the following steps:
    steps (a1) to (a3) as described above, that is to say a1) add a solution of the p-type semiconductor conjugate molecule, which comprises a p-type semiconductor conjugate molecule and a solvent, to a semiconductor nanostructure dispersion of type n comprising a semiconductor nanostructure of type n and a solvent; a2) stir the mixture obtained in (a1) at a temperature range between -20 ° C and 200 ° C, preferably between 0 ° C and 100 ° C, and a3) deposit the solution obtained in step (a2) on a substratum;
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    a step a4) of drying the wet film obtained in step (a3) by evaporating the solvents.
    After step (a4) a dry film is obtained; This preferred embodiment of the process of the invention relates to the irradiation of the dry film with UV-VIS radiation.
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    In a preferred embodiment, the dried film obtained has a thickness between 10 nm and 100 p, m. Preferably, the dried film obtained in step (a) has a thickness between 1 p, m and 10 p, m.
    In the present invention, the term "UV-VIS radiation" refers to a wavelength range between 100 nm and 800 nm. UV radiation is preferred in relation to a wavelength range between 200 nm and 350 nm.
    In a preferred embodiment, step b) is performed in the presence of an atmosphere containing oxygen. UV light of wavelength up to ~ 250 nm is mostly absorbed by O2 oxygen, so that O3 ozone is produced.
    The irradiation of step b) is performed using a laser source, a diode or a lamp. Preferably, UV-VIS irradiation is performed using a lamp.
    The wet or dry film can be partially or completely exposed to UV-VIS radiation. Preferably a mask is used for partially exposing the wet or dry film to UV-VIS radiation.
    UV-VIS irradiation of the films can be done by
    - rotational movement of the source of UV irradiation, that is to say including irradiation from all angular directions; irradiation at 90 ° (perpendicular to the film) is preferred; Y
    - a vertical and horizontal movement of the film
    The type n organic semiconductor obtained by the process of the invention can be used as part of an electrical or electronic device.
    In addition, the n-type organic semiconductor obtained by the process of the invention can be used as part of a thermoelectric generator.
    Unless defined otherwise, all the technical and scientific terms used herein have the same meaning as that usually understood by an expert in the field to which this invention belongs. Procedures and
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    materials similar or equivalent to those described herein in the implementation of the present invention. Throughout the description and claims, the word "comprise" and its variations are not intended to exclude other technical characteristics, additives, components, or stages. Objectives, advantages and additional features of the invention will become apparent to those skilled in the art upon examination of the description or can be learned by practicing the invention. The following examples and drawings are provided by way of illustration and are not intended to be limiting of the present invention.
    BRIEF DESCRIPTION OF THE DRAWINGS
    Figure 1. Scanning electron micrographs of the nanostructure of four representative CNT / P3HT nanocomposites (from the upper left to the lower right: CNT 30% by weight, CNT 80% by weight, CNT 30% by weight treated with acid and CNT at 30% by weight treated with UV for 60 s). Variable amounts of CNT and P3HT matrix beams are visible in all samples. Additionally, the 80% samples by weight contain Fe catalyst, and in the samples treated with UV, cut-off characteristics ("scrap") are visible.
    Figure 2. Topograph AFM of the four representative CNT / P3HT nanocomposites (from the upper left to the lower right: CNT 30% by weight, CNT 80% by weight, CNT 30% by weight treated with acid and 30% by weight CNT treated with UV for 60 s) shows that 80% by weight and UV treated samples have considerable roughness.
    Figure 3. Transmission X-ray micrograph measured at 399 eV, slightly above Ka (nitrogen). The darker areas correspond to an increased absorption, due to the presence of nitrogen.
    Figure 4. X-ray micrograph of transmission measured at 520 eV. The darkest areas correspond to an increased non-specific absorption of any element. Instead, these areas are indicative of a larger sample thickness.
    Figure 5. Transmission X-ray micrograph measured at 707 eV, slightly by
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    above La (iron). The darker areas correspond to an increased absorption caused by the presence of iron in the sample.
    Figure 6. Conductive AFM measurements of the four representative CNT / P3HT nanocomposites (from top left to bottom right: 30% CNT by weight, 80% CNT by weight, 30% CNT by weight treated with 30% by weight acid and CNT treated with UV for 60 s). The scale is proportional to the logarithm of the measured current.
    Figure 7. Histograms of the conductive AFM measurements of the four representative CNT / P3HT nanocomposites (from the upper left to the lower right: 30% CNT by weight, 80% CNT by weight, 30% CNT in weight treated with acid and CNT 30% by weight treated with UV for 60 s). The four main peaks are related to degraded P3HT (a), P3HT of increasing doping degree (b, c) and CNT (d).
    Figure 8. Dependence of thermoelectric properties of the CNT concentration for CNT as synthesized (black, continuous line) and acid treated CNT (blank squares, dashed line).
    Figure 9. Photograph of a first prototype device manufactured from five pnn pairs made of compounds at 20% by weight of CNT and 80% by weight on PET substrate. The device supplies a Seebeck voltage of ~ 170 p, V / K.
    Figure 10. Properties of the sample after UV irradiation during deposit.
    (a) Seebeck coefficient versus duration of UV treatment for samples containing 20% by weight of CNT (blank triangles) and CNT at 30% by weight (black circles). The lines serve as gluttony for the eye. Error bars represent the standard deviation.
    (b) Normalized absorbance (dashed-dotted lines) and PL spectra (continuous lines) of 20% by weight CNT samples that have been irradiated during time intervals.
    Figure 11. Optical micrographs of 30% by weight CNT compound as shown
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    I prepare (a), and after 60 s (b), 150 s (c) and 240 s (d) of UV irradiation. The scale bar is 200 p, m.
    Figure 12. Raman spectra of CNT samples at 30% by weight before (blank calculations) and after 60 s of UV irradiation (blank squares), and for a 70% CNT sample by weight (blank triangles ). The peaks marked at approximately 1300 cm-1 and 1600 cm-1 are related to the band D and G of the CNT, and the peak at approximately 1450 cm-1 with the symmetrical C = C elongation mode of P3HT.
    Figure 13. Dependence of the electrical conductivity of the duration of the UV treatment for samples at 20% by weight (blank triangles) and 30% by weight (black circles). Error bars represent the standard deviation.
    Figure 14. FTIR spectra measured by infrared spectroscopy by attenuated total reflectance (ATR) of P3HT solutions that have been treated with UV for different amounts of time (a, b) and a summary of relative peak heights plotted against time (C)
    Figure 15. Manufacture and proposed applications of the geometry of a device in which the advantages of the material presented are taken advantage of. The different layers are indicated as substrate (s), electrically conductive interconnection (c), wet film of solution of type p (p1), wet film of solution treated with UV (n1), dry film of type p (p2), film dry type n (n2).
    Figure 16. Output current (blank symbols) and output power (black symbols) for the device with 15 pairs of branches shown in figure 14.
    Figure 17. Stability of the electrical conductivity a (blank symbols) and the Seebeck S coefficient (black symbols) over time.
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    EXAMPLES
    Preparation of CNT / P3HT compounds
    Materials:
    Carbon nanotubes of multiple walls doped with nitrogen were synthesized from the feedstock of a saturated solution of acetonitrile / ferrocene by chemical vapor deposition (CVD). CNTs contain approximately 7% by weight of nitrogen, as determined by EELS / STEM analysis.
    Poly (3-hexylthiophene-2,5-diyl) (P3HT, Mw ~ 97 kg mol-1, Mw / Mn ~ 2,4, regioregularity> 90%), ortho-dichlorobenzene (oDCB) (99% ReagentPlus) and chloroform (> 99.9% CHROMASOLV) were obtained from Sigma Aldrich.
    Sample preparation.
    CNT was dispersed in oDCB at a concentration of 1 gl-1 and sonicated in ice water for 60 min (JP Selecta Ultrasons 50W). P3HT was dissolved in chloroform at a concentration of 20 gl-1 and an appropriate amount was added in three stages to the CNT dispersion, to create a mixture with the desired CNT concentration. After each addition, the mixture was sonicated an additional 30 min in ice water. After one day, a precipitate of undissolved residual carbon and sedimented CNT can be observed, the remaining solution was stable for months.
    1.5 ml of solution was dripped onto PET substrates and allowed to evaporate. Some samples were irradiated with 50 mWcm-2 of UV light directly after the solution tank in a Jelight UVO-Cleaner 42.
    Characterization of CNT / P3HT compounds
    Techniques:
    Electrical characterization. The Seebeck coefficient was measured at 300 K and conditions
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    atmospheric atmospheres with an SB1000 instrument equipped with a K2000 temperature controller from MMR Technologies using a thermal load of approximately 1-2 K and a constantan wire as internal reference. For each composition, six small samples of 5 mm by 1 mm of two independently prepared films were measured; Each measurement was repeated 10 times. The samples were contacted with silver paste from Agar Scientific.
    Electrical conductivity measurements were made on different samples of the same batch. Four silver paste contacts were placed in the corners of the 1 cm by 1 cm samples. The conductivity was measured with an Ecopia HMS-5000 Hall measurement system, using the van der Pauw method.
    Thermal volumetric conductivity. Samples were prepared for thermal conductivity measurements (1) solidifying 1 gl-1 CNT material combined in ODCB and 20 gl-1 P3HT in CHCl3 solutions, (2) compacting the material at room temperature and a pressure of 18, 5 kNcm-2 to form two round tablets of identical compressed material with a diameter of 13 mm, and (3) compressing the tablets in a press at 150 ° C and at a pressure of less than 7.4 kNcm-2. The density was estimated by measuring the volume and weight of the tablets of compressed material. The heat capacity and thermal diffusivity were measured at room temperature with a TPS 2500 S device from Hotdisk AB using an isotropic model.
    Physical characterization The sample thickness was measured using a KLA Tencor MicroXAM-100 optical surface profilometer for samples with CNT 50% by weight and below. Samples with a higher CNT concentration were measured using a KLA Tencor P16 + profilometer. The thickness of the sample varied between 15 p, m and 0.8 p, m, depending on the total solution concentration. For compounds with high% CNT weight, the samples contain a significant amount of vacuums and, consequently, the total amount of material is overestimated.
    Optical characterization The transmission spectra of the samples were measured using a SES Gra-5E elliptometer from Sopralab. Raman and photoluminescence spectra were measured in backscatter configuration with a LabRam HR800 (Horiba JobinYvon) spectrometer coupled to an Olympus confocal microscope, using wavelengths of
    excitation of 514 nm and 633 nm. Optical microphotographs were taken using an Olympus BX51 optical microscope and a DP20 microscope digital camera.
    Structural characterization. Scanning electron microscope was carried out using a FEI Quanta 200 FEG. The atomic force microscope (AFM) and current detection AFM were measured using an Agilent 5500LS instrument with a solid platinum tip from Rocky Mountain Nanotechnology. TXM was carried out on the MISTRAL beam line in the ALBA synchrotron. For this, the samples were drip deposited on copper grids.
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    Results
    Compounds with different stoichiometers and subsequent treatments were prepared. Table 1 shows the compositions and treatments applied to each compound.
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    Table 1:
    Compounds
    2.5 CNT; 5; 10; twenty; 30; 40; fifty; 60; 70; 80% by weight
    CNT treated with acid 5; 30; fifty; 70% by weight
    UV irradiated compounds for 20, 40, 60, 80 seconds at 20% by weight
    UV irradiated compounds for 10, 20, 30, 40, 50 60, 70, 80,
    90, 120, 150 and 240 seconds at 30% by weight
    Four representative CNT / P3HT compounds were selected and are summarized in Table 2.
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    Table 2: Representative CNT / P3HT compounds:
     (a) 30% CNT by weight  (b) 80% CNT by weight
     (c) CNT treated with 30% acid by weight  (d) CNT treated with UV for 60 s at 30% by weight
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    Figure 1 shows the scanning electron micrographs of the nanostructure of four representative CNT / P3HT nanocomposites given in Table 2 (from the upper left to the lower right: (a) 30% CNT by weight, (b) 80% CNT by weight, (c) 30% CNT by weight treated with acid, and (d) 30% CNT by weight treated with UV for 60 s). Variable amounts of CNT and P3HT matrix beams are visible in all samples. Additionally, samples at 80% by weight contain iron catalyst Fe, and in samples treated with UV, similar characteristics to residues are visible.
    Scanning electron microscopy (SEM) images of P3HT and CNT compounds of multiple walls doped with nitrogen with low content of CNT (c ~ 30% by weight) appear well dispersed, while samples with high content of CNT (c CNT at ~ 80% by weight) show agglomeration (figure 1a). In all cases, thick fibrillar structures with a diameter of 90 ± 30 nm are observed, which are probably bundles of CNT wrapped with polymer.
    Figure 2 shows AFM topography of the four representative CNT / P3HT nanocomposites (from the upper left to the lower right: 30% CNT by weight, 80% CNT by weight, 30% CNT by weight treated with acid and 30% by weight CNT treated with UV for 60 s) shows that 80% by weight and UV treated samples exhibit considerable roughness.
    In addition, atomic force microscope (AFM) images reveal an increase in surface roughness with increasing CNT content (Figure 2). The resulting films clearly show a fine fibrillar structure with an average beam diameter of 55 ± 15 nm, which is significantly smaller than for samples with high CNT content (Figures 1 and 2).
    Figures 3, 4 and 5 show transmission X-ray photomicrographs measured at 399 eV, 520 eV and 707 eV, respectively. The measurements shown in Figure 3 are slightly above the absorption edge Ka (nitrogen). The darker areas correspond to an increased absorption, due to the presence of nitrogen. The darkest areas shown in Figure 4 correspond to a greater non-specific absorption of any element. They are indicative, instead, of a greater (local) thickness of the sample.
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    The measurements shown in Figure 5 are slightly above the absorption edge La (iron). The darker areas correspond to an increased absorption caused by iron present in the sample.
    Transmission X-ray microscopy (TXM) is used to confirm that CNTs are distributed homogeneously throughout the thickness of the film, as well! as on the surface (figure 3, 4 and 5). The TXM also reveals the presence of iron-rich lumps in the sample, that is, residues of CNT synthesis.
    Figure 6 shows the AFM measurements in electric conductor mode of the four representative CNT / P3HT nanocomposites (from the top left to the bottom right: 30% CNT by weight, 80% CNT by weight, 30% CNT % by weight treated with acid and CNT at 30% by weight treated with UV for 60 s) and Figure 7 the histograms of said AFM measurements in conductive mode. The four main peaks are related to degraded P3HT (a), P3HT with increasing degree of doping (b, c) and CNT (d). Electrically, the compounds consist of highly conductive CNT-rich regions surrounded by polymer-rich regions that show conductivity around four orders of lower magnitude (Figures 6 and 7).
    Figure 8 shows the dependence of thermoelectric properties as a function of the CNT concentration for as synthesized (black circles, continuous line) and for CNT treated with acid (blank squares, broken line).
    (a) The electrical conductivity c exhibits a percolative behavior, which corresponds to the increase in several orders of magnitude at the time of additional a bit of weight% of CNT. At a high CNT content, a broth of c is observed for CNT as synthesized. The dotted line outlines the expected behavior for similar compounds prepared from normal, non-doped CNTs.
    (b) Correspondingly, S decreases steadily with the increase in the CNT concentration, and changes its sign to negative values at a concentration cs of 40% by weight. For higher CNT concentrations, S is saturated at approximately - 10 pVK "1. For CNT treated with acid, S is independent of the CNT concentration in the investigated range. The diagram added shows the measured composition range
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    full.
    (c) Resulting power factor S2c. For CNT as synthesized, two regions are evident, one below cs, where the compound has properties of type p, and another above cs, where the material is type n.
    (d) Average intensity of PL between 675 nm and 725 nm, for samples excited at 514 nm. The diagram added shows two representative spectra with c = 0% by weight and c = 80% by weight. Error bars indicate the standard deviation for a sampling of 2 batches of 6 samples each.
    Macroscopically, the films deposited by dripping on PET substrates have an electrically percolating behavior depending on the CNT content, with a percolation threshold around cp ~ 3.5% by weight (Figure 8a). This threshold points to relatively well dispersed carbon nanotubes, according to the SEM, AFM and TXM data shown in Figure 1.
    For thermoelectric materials, the figure of dimensionless merit ZT = S2 <jT / k is usually used as a reference, where S is the Seebeck coefficient (S> 0 for semiconductors of type p <0 for type n), to the electrical conductivity, k the thermal conductivity, and T the average absolute temperature.
    The macroscopic c also increases sharply, in this case by five orders of magnitude, when comparing the pure polymer and the compounds with weight fractions above the percolation. Interestingly, the Seebeck coefficient varies from that of the pure polymer (~ 1000 pVK "1) to that of the CNT (~ -10 pVK" 1) and correlates well with the percolation threshold observed for a (Figure 8b). Surprisingly, at approximately cs ~ CNT content at 40% by weight, the Seebeck coefficient changes sign. The corresponding power factor has two regimes, therefore, separated by a value of zero. Simple modules can be made using these compounds, with branches p with c = 20% by weight, and branches n with c = 80% by weight. An example consisting of five pairs of said branches is shown in Figure 9 and provides a 170 p, VK-1 thermotension that is close to the sum of the Seebeck coefficients of the constituent branches.
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    Since cp << cs, the majority carriers for CNT at c ~ 25% by weight are voids, or, in other words, the voids are being transported through the CNTs, which is the most electrically conductive part of the compound. P3HT is effectively doping the CNT. This is supported by photoluminescence (PL) inactivation experiments (Figure 8d), which indicate that there is a strong transfer of photoinduced charge between P3HT and CNT.
    The observed phenomenology can be explained well in terms of a simple band model, which assumes that the semiconductor CNTs are being codopated, on the one hand, by nitrogen atoms incorporated in a substitute way, and on the other hand, by P3HT adsorbed on the surface of the CNT. The Fermi level and therefore the density of majority cargo carriers are determined below by the specific amount of dopants. In addition, these compounds show thermochromic solution when heated. After increasing the temperature, the solution of the compound changes from a characteristic dark purple, indicative of crystalline P3HT and / or stacked in the direction of the% orbitals, to the bright orange coloration associated with well dissolved P3HT (amorphous / isolated). Unfortunately, this change is not preserved through the transition to the dry film, since no changes in thermoelectric properties are observed. Conversely, a reference P3HT solution shows no change during preparation and subsequent heating.
    For samples that were irradiated with UV while drying using a low pressure mercury vapor lamp, the Seebeck coefficient decreases continuously as a function of the irradiation time for the investigated samples, which contain 20% CNT by weight and at 30% by weight (figure 10a). For samples at 30% by weight, S becomes negative after 60 s of UV irradiation.
    To understand the impact of UV irradiation on thermoelectric properties, its effect on the structural and optical properties of the compounds was investigated below.
    The optical microscope indicates that long exposure times (> 120 s) produce visibly degraded samples (Figure 11).
    AFM also suggests an increase in surface roughness (Figure 2), while SEM
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    shows the appearance of small curly cuts (figure 1), which are electrically insulating (figure 6 and 7), which are attributed to degraded polymer.
    Raman scattering results suggest that UV light has no negative effect on CNTs (as measured by the relationship of D and G bands, figure 12). In general, long exposure times clearly degrade the samples and, as a result, the macroscopic electrical conductivity also decreases slightly (Figure 13).
    Figure 10b shows the normalized absorption and PL intensities of four samples irradiated for 0 s, 60 s, 150 s and 240 s. The degradation mentioned above is seen in this case as an absorption with displacement towards the blue, which probably occurs due to the reduction in the length of conjugation of the polymer. The inactivation of the PL described above is, at the time of UV irradiation, much less pronounced, demonstrating a lower degree of charge transfer between degraded polymer chains and CNT, with the concomitant lower degree of doping p of the CNT.
    Figure 10b also shows that there are two clear regimes: for low exposure times (<60 s), there is little degradation of the polymer (no photobleaching, no absorption with displacement towards the blue, high degree of inactivation of the PL) but a strong change of electronic properties, as seen by changing the Seebeck sign. Instead, long exposure times (> 120 s) result in the complete degradation of the polymer with strong negative effects on the electronic properties as well. The Fourier transform infrared spectra (FTIR) shown in Figure 14 support this observation, and provide evidence that UV treatment attacks both the carbon double bonds of the thiophene ring, and the alkyl side chains, influencing the doping not only reducing conjugation, but also altering the CNT-P3HT interaction.
    The characteristic peaks of P3HT are related to group excitations = CH (3055 cm-1), C-H2 (2924 cm'1, 2856 cm'1, 1454 cm'1), C-H3 (2954 cm'1, 2870 cm'1, 1377 cm'1) and the thiophene ring links C = C (1560 cm'1, 1512 cm'1, 1460 cm'1). A slight decrease in the absorption of these modes is observed with increasing UV treatment time (a, c). This decrease is more pronounced for longer treatment durations (b, c). However, then an additional effect is observed due to the
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    solvent
    A thermoelectric module manufactured from a single solution with p and n branches (irradiated with UV) was made. Figure 15 illustrates a prototype thermoelectric module and some intended applications that are implemented through a toroidal geometry of the module.
    The fabrication is detailed in Figure 15. First, a uniform wet layer of the compound is deposited on a substrate (s), and part of it is irradiated with UV during drying, resulting in a wet film without treatment (p1 ) and a wet film that received UV treatment (n1). Second, the individual branches (p2, n2) of the dry film are defined by appropriate cuts. Branches of type p and n were connected with an electric conductor (c) to reinforce the bridge region. Next, the device is folded in a spiral, and adjacent pairs are electrically connected in series by depositing contacts (c). Finally, the ends of this spiral come together to form a bull. Possible applications for this geometry are in the form of a single bull, an extended spiral and a bracelet.
    When one side of this module comprising 15 double branches (thermocouples) joins a glass filled with ice water, leaving the other side at room temperature, a voltage of 5 mV is generated corresponding to 217.4 pVK "1 or 14.5 p, V K-1 per pair A graphical representation of current and output power versus voltage is given in Figure 16. The module supplies ~ 2 nA at 5 mV Seebeck voltage. Alternatively, it is possible to connect a greater number of branches to collect, for example, residual heat from a pipe, for this, the spiral itself can be wound in another spiral.
    Importantly, the thermal bulk conductivity was measured in selected samples and it is verified that k only increases slightly from 0.29 Wm'1K'1 for pure P3HT to 0.55 Wm'1K'1 for a compound ac = 80 % by weight (see table 3). The non-optimized ZT values vary. Then, about 10 "3 to 10" 5 for the compound of type p and type n, respectively.
    All samples were prepared, measured and stored under normal atmospheric conditions. Figure 17 shows the results of repeated electrical measurements carried out over a period of up to 600 days. For the compounds of
    type n, the conductivity was stabilized at 41% of the initial value, with samples with both a high CNT content and UV treated, both following a similar trend. The negative Seebeck coefficient of each sample of type n remained stable and without significant changes observed after 240 days. In the same amount of time, the 5 Seebeck coefficient of p-type samples decreased to 40% of the initial value and electrical conductivity to 11% of the initial value.
    Table 3. Measured properties used to determine the thermal conductivity k of samples of P3HT-CNT pads type 13 mm in diameter.
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     Density p [g cm'3] Specific heat Cp [J kg'1 K'1] Thermal diffusivity at [mm2 s' 1] Thermal conductivity k [Wm-1K-1]
     Pure P3HT  1.05 ± 0.01 1496.79 ± 14.77 0.18 ± 0.00 0.29 ± 0.01
     30% CNT by weight  1.17 ± 0.01 1193.52 ± 2.08 0.35 ± 0.01 0.49 ± 0.02
     CNT 30% by weight treated with acid  1.13 ± 0.01 1233.62 ± 3.78 0.29 ± 0.00 0.40 ± 0.03
     80% CNT by weight  1.21 ± 0.01 947.72 ± 1.90 0.48 ± 0.01 0.55 ± 0.04
    权利要求:
    Claims (17)
    [1]
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    1. A method of obtaining an organic semiconductor type n characterized in that the procedure comprises the following steps:
    a) preparing a film of a p-type organic semiconductor on a substrate in which said p-type organic semiconductor comprises
    • a n-type semiconductor nanostructure that varies by weight percentage between 0.1% and 60%; Y
    • a p-type semiconductor conjugate molecule;
    and wherein said n-type semiconductor nanostructure is dispersed in the p-type semiconductor conjugate molecule; Y
    b) irradiate the film obtained in step (a) by UV-VIS radiation with a power between 1 mW / cm2 and 100 mW / cm2 and an exposure time between 0.1 s and 600 s.
    [2]
    2. The method according to claim 1, wherein the n-type semiconductor nanostructure is selected from the list consisting of carbon nanotubes doped with N, graphene sheets and graphite nanolamines doped with N, graphene nanocins doped with N, fulerenes, phosphorus doped silicon nanowires, tellurium based nanowires such as Bi2Te3 nanowires or PbTe nanowires, zinc oxide based nanowires, titanium oxide based nanowires, and a combination thereof .
    [3]
    3. The method according to any one of claims 1 or 2, wherein the p-type semiconductor conjugate organic molecule is selected from polyalkylthiophenes, polyfluorenes, polyaniline, polyacetylene, polyphenylenevinylene, tetracyanoquinodimethane, tetrathiafulvalene and a combination thereof.
    [4]
    4. The method according to claim 3, wherein the p-type semiconductor conjugated organic molecule is poly (3-hexylthiophene), poly (3-dodecylthiophene-2,5-diyl) or poly (9,9-dioctylfluorene ).
    [5]
    5. The method according to any of claims 1 to 4, wherein the n-type semiconductor nanostructure varies in a weight percentage of between 20% and 40%.
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    [6]
    6. The process according to any of claims 1 to 5, wherein the substrate is flexible and wherein the substrate is selected from polyethylene terephthalate, polyethylene naphthalate, polyimide, polyethylene, polystyrene, poly (chloride of vinyl), polytetrafluoroethylene, polypropylene, polyurethane, polyvinylidene fluoride and a combination thereof.
    [7]
    7. The method according to any one of claims 1 to 6, wherein step a) comprises the following steps:
    a1) adding a p-type semiconductor conjugate molecule solution comprising a p-type semiconductor conjugate molecule and a solvent, to a n-type semiconductor nanostructure dispersion comprising a n-type semiconductor nanostructure and a solvent;
    a2) stir the mixture obtained in (a1) at a temperature range between -20 ° C and 200 ° C; and a3) deposit the solution obtained in step (a2) on a substrate.
    [8]
    8. The method according to claim 7, wherein step (a2) is performed at a temperature range between 0 ° C and 100 ° C.
    [9]
    9. The method according to any of claims 7 or 8, characterized in that it comprises a step a1 '), between step a1) and step a2), of adding a surfactant to the mixture obtained in (a1).
    [10]
    10. The method according to any of claims 7 to 9, wherein the wet film obtained in step (a3) is between 10 p, m and 1000 p, m thick.
    [11]
    11. The method according to claim 10, wherein the wet film obtained in step (a3) has a thickness between 100 p, m and 1000 m.
    [12]
    12. The method according to any of claims 1 to 11, wherein step a) comprises the following steps:
    steps (a1) to (a3) according to any of claims 6 or 7; Y
    a step (a4) of drying the wet film obtained in step (a3) by evaporating the
    solvents
    [13]
    13. The method according to claim 12, wherein the dried film obtained in step (a4) has a thickness between 10 nm and 100 p, m,
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    [14]
    14. The method according to claim 13, wherein the dried film obtained in step (a) has a thickness between 1 p, m and 10 p, m.
    [15]
    15. The method according to any of claims 1 to 14, wherein the step (b) is performed by UV-VIS radiation with a power between 40 mW / cm2 and 60
    mW / cm2 and an exposure time of between 50 s and 100 s.
    [16]
    16. The method according to any of claims 1 to 15, wherein step (b) is performed in the presence of an oxygen-containing atmosphere.
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    [17]
    17. The method according to any one of claims 1 to 16, wherein step (b) is performed using a laser source, a diode or a lamp.
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    同族专利:
    公开号 | 公开日
    EP3381069A1|2018-10-03|
    ES2613546B1|2018-02-28|
    WO2017089351A1|2017-06-01|
    EP3381069B1|2019-10-30|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO2012142269A1|2011-04-12|2012-10-18|Nanocomp Technologies, Inc.|Nanostructured material-based thermoelectric generators and methods of generating power|
    WO2014152570A2|2013-03-14|2014-09-25|Wake Forest University|Thermoelectric apparatus and articles and applications thereof|
    CN107681043B|2017-09-15|2020-04-21|武汉理工大学|Bismuth telluride-based composite thermoelectric material of flexible thermoelectric device and preparation method thereof|
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