CN110993721A - Photosensitive thin film transistor and preparation method thereof - Google Patents
Photosensitive thin film transistor and preparation method thereof Download PDFInfo
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- H01L31/08—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors
- H01L31/10—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors characterised by potential barriers, e.g. phototransistors
- H01L31/101—Devices sensitive to infrared, visible or ultraviolet radiation
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- H01L31/1136—Devices sensitive to infrared, visible or ultraviolet radiation characterised by field-effect operation, e.g. junction field-effect phototransistor being of the conductor-insulator-semiconductor type, e.g. metal-insulator-semiconductor field-effect transistor the device being a metal-insulator-semiconductor field-effect transistor
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Abstract
The invention belongs to the technical field of semiconductor devices, and particularly relates to a photosensitive thin film transistor and a low-temperature preparation method thereof. The photosensitive thin film transistor adopts the perovskite quantum dots as photosensitive materials, and the device can respond to light with different wavelengths by changing the proportion of halogen elements in the perovskite quantum dots; meanwhile, the preparation method of the photosensitive thin film transistor comprises the following steps: atomic layer deposition for preparing Al2O3The gate dielectric is used for growing an amorphous indium gallium zinc oxide (a-IGZO) channel layer through magnetron sputtering, perovskite quantum dots are prepared through a spin-coating method, and source and drain electrodes are prepared through electron beam evaporation; the long temperature of all the processes does not exceed 40 ℃, and the high-performance photosensitive thin film transistor can be obtained without heat treatment in the device preparation process. The invention can be applied to the fields of flexible electronics, photoelectric detection and the like.
Description
Technical Field
The invention belongs to the technical field of semiconductor devices, and particularly relates to a photosensitive thin film transistor and a low-temperature preparation method thereof.
Background
The photoelectric detector mainly comprises photosensitive elements, and can detect ultraviolet light, infrared light and visible light according to different forbidden band widths of photosensitive materials. The photosensitive material in the ultraviolet detector mainly adopts wide-bandgap semiconductor, and can be applied to ultraviolet flame monitoring, material curing, sterilization and disinfection and the like [1, 2 ]]. The infrared detector mainly adopts PbS, doped Si, Ge and Hg1-xCdxTe and other materials, and has already been mature applied in aspects of missile guidance and the like [3-5 ]]. The visible light detector mainly adopts CdS, CdSe, Si, Ge and the like as materials, and can be applied to ray measurement, industrial automatic control, photometric measurement and the like [6-8 ]]. However, it is still difficult for the current visible light detector to cover the whole visible light, so that a new photosensitive material is adopted to prepare a device responding to any wavelength of the visible light, and thus a series of detection devices covering the whole visible light waveband can be obtained, which is a problem to be solved urgently.
As a new generation of photoelectric materials, halogen perovskite quantum dots have high quantum yield, continuously adjustable band gap and strong visible light absorption capacity, and are widely applied to the fields of light emitting diodes, solar cells, photoelectric detection and the like [9, 10 ]. However, the perovskite quantum dots have poor stability in the environment, and are easy to deteriorate when in contact with water and oxygen in the air, so that the photoresponse characteristic is lost, and therefore, how to design the device structure is also one of the research problems to realize stable photoresponse under the condition of ensuring that the device performance is not degraded.
Flexible electronic devices are portable and easy to carry, have relatively low process cost and high flexibility, and have been widely used in the fields of displays, wearable electronic devices, artificial skin, and the like. However, it is still difficult to directly prepare a conventional photodetector on a flexible substrate and ensure that the performance of the conventional photodetector is not degraded [11-13 ].
Reference to the literature
[1]C. Xieet al., "Recent Progress in Solar-Blind Deep-UltravioletPhotodetectors Based on Inorganic Ultrawide Bandgap Semiconductors,"Advanced Functional Materials,Review vol. 29, no. 9, p. 40, Feb 2019, Art. no.1806006.
[2]Y. Qinet al., "Review of deep ultraviolet photodetector based ongallium oxide,"Chinese Physics B,vol. 28, no. 1, 2019.
[3]A. A. M. El-Amiret al., "Silicon-compatible Mg2Si/Si n-p photodiodeswith high room temperature infrared responsivity,"Materials Science in Semiconductor Processing,vol. 102, 2019.
[4]M. Liu, C. Wang, and L.-Q. Zhou, "Development of small pixel HgCdTeinfrared detectors,"Chinese Physics B,vol. 28, no. 3, 2019.
[5]D. Marris-Moriniet al., "Germanium-based integrated photonics fromnear- to mid-infrared applications,"Nanophotonics,vol. 7, no. 11, pp. 1781-1793, 2018.
[6]Z. H. Zhao and Y. Dai, "Piezo-phototronic effect-modulated carriertransport behavior in different regions of a Si/CdS heterojunctionphotodetector under a Vis-NIR waveband,"Phys Chem Chem Phys,vol. 21, no.18, pp. 9574-9580, May 8 2019.
[7]T. Zhang, J. Wang, L. Yu, J. Xu, and I. C. P. Roca, "Advanced radialjunction thin film photovoltaics and detectors built on standing siliconnanowires,"Nanotechnology,vol. 30, no. 30, p. 302001, Mar 8 2019.
[8]G. Li, Y. Jiang, Y. Zhang, X. Lan, T. Zhai, and G.-C. Yi, "High-performance photodetectors and enhanced field-emission of CdS nanowire arrayson CdSe single-crystalline sheets,"J. Mater. Chem. C,vol. 2, no. 39, pp.8252-8258, 2014.
[9]K. Wang, D. Yang, C. Wu, M. Sanghadasa, and S. Priya, "Recent progressin fundamental understanding of halide perovskite semiconductors,"Progress in Materials Science,vol. 106, 2019.
[10]L. Chen, J. Cai, J. Li, S.-P. Feng, G. Wei, and W.-D. Li, "Nanostructured texturing of CH3NH3PbI3perovskite thin film on flexiblesubstrate for photodetector application,"Organic Electronics,vol. 71, pp.284-289, 2019.
[11]H. M. S. Ajmalet al., "High-Performance Flexible UltravioletPhotodetectors with Ni/Cu-Codoped ZnO Nanorods Grown on PET Substrates,"Nanomaterials (Basel),vol. 9, no. 8, Jul 25 2019.
[12]K. Y. Kimet al., "Flexible narrowband organic photodiode with highselectivity in color detection,"Nanotechnology,vol. 30, no. 43, p. 435203,Oct 25 2019.
[13]P. Pataniyaet al., "Paper-Based Flexible PhotodetectorFunctionalized by WSe2Nanodots,"ACS Applied Nano Materials,vol. 2, no. 5,pp. 2758-2766, 2019.。
Disclosure of Invention
In order to solve the problems, the invention provides a photosensitive thin film transistor with good photosensitivity and stability and a low-temperature preparation method thereof.
The photosensitive thin film transistor provided by the invention has the following structure from bottom to top in sequence: the device comprises a back gate electrode, a gate dielectric layer, a conductive channel and a source drain electrode, wherein the perovskite quantum dot is used as a photosensitive material and is positioned in the middle of the conductive channel.
Preferably, the back gate electrode can be heavily doped Si, AZO, FTO, ITO, Au or Al; when the heavily doped Si is used as a back gate electrode, the Si is also used as a substrate of the device; when other heavily doped semiconductor or metal materials are used as the back gate electrode, the substrate of the device can be glass, a PI film or PET plastic.
Preferably, the perovskite quantum dot has a chemical general formula ABX3Wherein A may be CH3NH3(MA)、CH5N2(FA) or Cs, B may be Pb or Sn, and X may be one or two of Cl, Br and I.
Preferably, the source and drain electrode material can be Cr/Au, Ti/Au, Ni/Au, ITO, AZO or Mo.
The invention provides a low-temperature preparation method of a photosensitive thin film transistor, which comprises the following specific steps:
(1) growing Al on the upper surface of the back gate electrode by adopting an atomic deposition technology2O3A gate dielectric layer;
(2) growing and etching the upper surface of the gate dielectric layer by adopting a magnetron sputtering technology to obtain an IGZO conductive channel;
(3) preparing perovskite quantum dots in the middle of the IGZO channel by adopting a spin-coating method;
(4) the source-drain electrodes were prepared using electron beam evaporation.
Preferably, in the preparation method, Al grows2O3When the grid dielectric layer is prepared, the oxygen source is oxygen plasma, the aluminum source is trimethyl aluminum (TMA), the pulse of the trimethyl aluminum is 0.1-2s, the pulse of the oxygen plasma is 0.1-10s, the purging time of nitrogen each time is 10-30s, the growth temperature is 25-35 ℃, and the thickness of the prepared grid dielectric layer is 20-150 nm.
Preferably, in the preparation method, when the IGZO conductive channel is prepared, the air pressure of a cavity of the magnetron sputtering is kept at 0.5-2 Pa, the temperature is room temperature, and the thickness of the prepared conductive channel is 30-80 nm.
Preferably, in the preparation method, the perovskite quantum dot is prepared by a solution method, the band gap width of the quantum dot is changed by changing the proportion of halogen elements, and the prepared quantum dot is purified by methyl acetate high-speed centrifugation.
Compared with the prior art, the invention has the following advantages:
in the preparation method of the photosensitive transistor, the temperature is lower than 40 ℃, and the high-performance photosensitive characteristic can be obtained without subsequent annealing, so that the flexible photosensitive thin film transistor can be directly obtained. According to the invention, the halogen perovskite quantum dots are used as photosensitive materials, and the band gap width of the perovskite quantum dots is changed by changing the proportion of halogen elements, so that the transistors responding to light with different wavelengths in a visible light range can be prepared. As the perovskite quantum dots are easy to deteriorate in the water-oxygen environment, the perovskite quantum dots are placed in the middle of the a-IGZO channel, so that the contact with air is isolated, and the stability of the device can be greatly improved.
Drawings
FIG. 1 is a schematic view of a structure of a photosensitive TFT prepared according to the present invention.
FIG. 2 is a graph showing transfer characteristics of the devices prepared in examples 1 (a) and 2 (b) under different wavelengths of light.
FIG. 3 shows the ratio of dark current to light at different wavelengths for example 1 and example 2.
Detailed Description
The invention is further described below by means of specific embodiments in conjunction with the accompanying drawings.
Example 1
The photosensitive material adopted in the embodiment is CsPbBr3And (4) quantum dots.
As shown in fig. 1, the photosensitive thin film transistor provided by the present invention has the following structure from bottom to top: the structure comprises a back gate electrode 10, a gate dielectric layer 20, a conducting channel 30 and a source-drain electrode 50, wherein the perovskite quantum dots 40 are used as photosensitive materials and are positioned in the middle of the conducting channel. The preparation process comprises the following steps:
(1) heavily doped p-type silicon is selected as the back gate electrode 10, the resistivity is less than 0.005 Ω & cm, and acetone, isopropanol and deionized water are sequentially used for ultrasonic cleaning before use.
(2) The gate dielectric layer 20 is Al prepared by atomic layer deposition technology2O3The oxygen source of the film is oxygen plasma, the aluminum source of the film is Trimethylaluminum (TMA), the TMA temperature, the oxygen gas flow rate and the plasma generation power are respectively set to be 18 ℃, 150 sccm and 2500W, the growth temperature is 30 ℃, and the growth thickness is 40 nm.
(3) The conductive channel 30 is an a-IGZO thin film prepared by magnetron sputtering, the selected target is an IGZO target with the atomic ratio of In to Ga to Zn to O = 1 to 4, the total growth thickness is 40 nm, and the working pressure, the radio frequency power, the argon gas flow and the oxygen gas flow are respectively set to be 0.88 Pa, 110W, 48 and 2 sccm.
(4) Preparation of perovskite quantum dots 40: by using PbBr2CsPbBr is prepared by one-step method by using CsBr as raw material3And (4) quantum dots. First, 0.02 mmol of PbBr was taken2And CsBr, adding 5 ml of dimethylformamide, 0.5 ml of oleic acid and 0.25 ml of oleylamine, and carrying out ultrasonic treatment at 40 ℃ until the solution is clear and transparent to form a precursor solution. 1 ml of the precursor solution is added into 10ml of anhydrous toluene which is stirred at a high speed to form a quantum dot solution. In order to remove impurities in the solution, the quantum dot solution and methyl acetate are mixed according to the volume ratio of 1:3, high-speed centrifugation is carried out for purification, and the obtained quantum dots are dispersed into n-hexane after twice purification to obtain CsPbBr for device preparation3A quantum dot solution. After the a-IGZO thin film grows to 20nm, the perovskite quantum dots are spin-coated on the thin film, and then the subsequent 20nm is grown to form a composite channel of the a-IGZO and the quantum dots.
(5) And (3) forming a pattern by ultraviolet exposure of the negative photoresist under the mask, preparing a 30nm Ti/70nm Au double-layer film serving as a source/drain electrode 50 by adopting electron beam evaporation, and finally removing the redundant photoresist by acetone by adopting a stripping process to obtain the photosensitive thin film transistor with the structure shown in the figure 1.
Example 2
The photosensitive material adopted in the embodiment is CsPbI3And (4) quantum dots. The preparation process comprises the following steps:
(1) heavily doped p-type silicon is selected as the back gate electrode 10, the resistivity is less than 0.005 Ω & cm, and acetone, isopropanol and deionized water are sequentially used for ultrasonic cleaning before use.
(2) The gate dielectric layer 20 is Al prepared by atomic layer deposition technology2O3The oxygen source of the film is oxygen plasma, the aluminum source of the film is TMA, the temperature of TMA, the flow rate of oxygen gas and the plasma generation power are respectively set to be 18 ℃, 150 sccm and 2500W, the growth temperature is 30 ℃, and the growth thickness is 40 nm.
(3) The conductive channel 30 is an amorphous IGZO thin film prepared by magnetron sputtering, the selected target is an IGZO target with the atomic ratio of In to Ga to Zn to O = 1 to 4, the total growth thickness is 40 nm, and the working pressure, the radio frequency power, the argon gas flow and the oxygen gas flow are respectively set to be 0.88 Pa, 110W, 48 and 2 sccm.
(4) Preparation of perovskite quantum dots 40: by using PbBr2CsPbBr is prepared by one-step method by using CsBr as raw material3Quantum dots;
first, 0.02 mmol of PbBr was taken2And CsBr, adding 5 ml of dimethylformamide, 0.5 ml of oleic acid and 0.25 ml of oleylamine, and carrying out ultrasonic treatment at 40 ℃ until the solution is clear and transparent to form a precursor solution. 1 ml of the precursor solution is added into 10ml of anhydrous toluene which is stirred at a high speed to form a quantum dot solution. In order to remove impurities in the solution, the quantum dot solution and methyl acetate are mixed according to the volume ratio of 1:3, high-speed centrifugation is carried out for purification, and the obtained quantum dots are dispersed into n-hexane after twice purification to obtain CsPbBr for device preparation3A quantum dot solution;
0.4 mmol of PbI is taken2Dissolving the powder in 10ml of n-dodecane, 1 ml of oleic acid and 0.5 ml of oleylamine, and performing ultrasonic treatment at 40 ℃ until the solution is clear and transparent to form PbI2A precursor liquid. Will PbI2Precursor solution and purified CsPbBr3The quantum dot solution is mixed according to the volume ratio of 1:1 and stirred at high speed. Then mixing the displaced solution and methyl acetate according to the volume ratio of 1:3, carrying out high-speed centrifugal purification, dispersing the obtained quantum dots into n-hexane after twice purification to obtain CsPbI3A quantum dot solution;
after the a-IGZO thin film grows to 20nm, spin-coating CsPbI on the thin film3And (3) growing the perovskite quantum dots, and then growing the subsequent 20nm to form a composite channel of the a-IGZO and the quantum dots.
(5) And (3) forming a pattern by ultraviolet exposure of the negative photoresist under the mask, preparing a 30nm Ti/70nm Au double-layer film serving as a source/drain electrode 50 by adopting electron beam evaporation, and finally removing the redundant photoresist by acetone by adopting a stripping process to obtain the photosensitive thin film transistor with the structure shown in the figure 1.
And (3) performance testing:
fig. 2 shows the transfer characteristics of the two embodiments under different wavelengths and the same light intensity. For CsPbBr in example 13When the wavelength of the irradiated TFT is more than 620 nm, the transfer characteristic curve of a Thin Film Transistor (TFT) with the quantum dot and a-IGZO composite channel is almost unchanged, which shows that the Thin Film Transistor does not respond to light with the wavelength more than 620 nm. When the wavelength of the irradiation light is less than 580 nm, the off-current of the device is increased, the threshold voltage moves towards the negative direction, and the subthreshold swing is increased, which indicates that the wavelength is less than 580 nmUnder the illumination of light with the wavelength less than 580 nm, photogenerated carriers are generated in the channel. For CsPbI in example 23The TFT of the quantum dot and a-IGZO composite channel has photoresponse when the wavelength of irradiating light is 700 nm, and the smaller the wavelength of the irradiating light of the two devices is, the stronger the photoresponse is, which shows that the perovskite quantum dot can generate more photogenerated carriers by the short-wavelength light irradiation with higher energy.
Fig. 3 is a graph showing the change in the ratio of optical dark current with the wavelength of the illumination light for the devices of the two embodiments. As can be seen, CsPbBr3The light-dark current ratio of the TFT of the quantum dot and IGZO composite channel under the irradiation of 580 nm wavelength is-10, and CsPbI3The light-dark current ratio of the TFT of the quantum dot and IGZO composite channel under the irradiation of 700 nm wavelength can reach-10. The result shows that by changing the halogen element in the perovskite quantum dot, the device responding to the visible light with different wavelengths can be obtained, and the light-dark current ratio of the device can reach more than 10.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. Various modifications and alterations to this invention will become apparent to those skilled in the art upon reading the foregoing description. Accordingly, the scope of the invention should be determined from the following claims.
Claims (8)
1. The photosensitive thin film transistor is characterized in that the structure of the photosensitive thin film transistor sequentially comprises from bottom to top: the back gate electrode, gate dielectric layer, conducting channel and source drain electrode, wherein the photosensitive material adopts perovskite quantum dot, is located the middle of the conducting channel.
2. The photoactive thin-film transistor of claim 1, wherein the back-gate electrode is heavily doped Si, AZO, FTO, ITO, Au or Al; when the back gate electrode is heavily doped Si, the back gate electrode is also a substrate of the device; when the back gate electrode is the rest heavily doped semiconductor or metal material, the substrate of the device is glass, PI film or PET plastic.
3. A photoactive thin film transistor according to claim 1 wherein the perovskite quantum dots have the general chemical formula: ABX3Wherein A is CH3NH3(MA)、CH5N2(FA) or Cs, B is Pb or Sn, and X is one or two of Cl, Br and I.
4. The photosensitive thin film transistor of claim 1, wherein the source and drain electrode material is Cr/Au, Ti/Au, Ni/Au, ITO, AZO, or Mo.
5. The low-temperature preparation method of the photosensitive thin film transistor according to any one of claims 1 to 4, comprising the steps of:
(1) growing Al on the upper surface of the back gate electrode by adopting an atomic deposition technology2O3A gate dielectric layer;
(2) growing and etching the upper surface of the gate dielectric layer by adopting a magnetron sputtering technology to obtain an IGZO conductive channel;
(3) preparing perovskite quantum dots in the middle of the IGZO channel by adopting a spin-coating method;
(4) the source-drain electrodes were prepared using electron beam evaporation.
6. The low temperature fabrication method of photosensitive TFT according to claim 5, wherein the grown Al is2O3When the grid dielectric layer is used, the oxygen source is oxygen plasma, the aluminum source is trimethyl aluminum, the pulse of the trimethyl aluminum is 0.1-2s, the pulse of the oxygen plasma is 0.1-10s, the purging time of nitrogen each time is 10-30s, and the growth temperature is 25-35 ℃; the thickness of the gate dielectric layer is 20-150 nm.
7. The low-temperature preparation method of the photosensitive thin film transistor according to claim 5, wherein during the preparation of the IGZO conductive channel, the pressure of a cavity of magnetron sputtering is kept at 0.5-2 Pa, the temperature is room temperature, and the thickness of the conductive channel is 30-80 nm.
8. The low-temperature preparation method of the photosensitive thin film transistor according to claim 5, wherein the perovskite quantum dot is prepared by a solution method, the band gap width of the quantum dot is changed by changing the proportion of halogen elements, and the prepared quantum dot is purified by methyl acetate through high-speed centrifugation.
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