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WO2014148830A1 - Procédé pour fabriquer un précurseur d'oxyde de zinc, précurseur d'oxyde de zinc obtenu par celui-ci, et couche mince d'oxyde de zinc - Google Patents

Procédé pour fabriquer un précurseur d'oxyde de zinc, précurseur d'oxyde de zinc obtenu par celui-ci, et couche mince d'oxyde de zinc Download PDF

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WO2014148830A1
WO2014148830A1 PCT/KR2014/002337 KR2014002337W WO2014148830A1 WO 2014148830 A1 WO2014148830 A1 WO 2014148830A1 KR 2014002337 W KR2014002337 W KR 2014002337W WO 2014148830 A1 WO2014148830 A1 WO 2014148830A1
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zinc
zinc oxide
thin film
oxide thin
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김홍두
황재은
이민규
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/02—Oxides; Hydroxides
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D30/00—Field-effect transistors [FET]
    • H10D30/60—Insulated-gate field-effect transistors [IGFET]
    • H10D30/67—Thin-film transistors [TFT]
    • H10D30/674—Thin-film transistors [TFT] characterised by the active materials
    • H10D30/6755—Oxide semiconductors, e.g. zinc oxide, copper aluminium oxide or cadmium stannate
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F71/00—Manufacture or treatment of devices covered by this subclass
    • H10F71/138—Manufacture of transparent electrodes, e.g. transparent conductive oxides [TCO] or indium tin oxide [ITO] electrodes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM

Definitions

  • the present invention relates to a method for preparing a zinc oxide precursor, to a zinc oxide precursor and a zinc oxide thin film obtained therefrom, and more particularly to a method for producing zinc hydroxide, which is a kind of zinc oxide precursor, with high purity crystals and It relates to an invention for forming a zinc oxide thin film that can be used for use in oxide semiconductors and the like by low temperature firing using the prepared zinc hydroxide.
  • the next-generation display is to use the printing process in an effort to achieve a low price, in order to achieve this, the backplane by the semiconductor must also be formed by a solution process.
  • a solution process In particular, in manufacturing a semiconductor, efforts to use an oxide semiconductor capable of solution processing in a method using silicon are accelerating.
  • a target material such as indium-gallium-zinc oxide (IGZO)
  • IGZO indium-gallium-zinc oxide
  • the process of liquefying an oxide semiconductor is essential, and in order to become a semiconductor required for a flexible display, it is necessary to show certain characteristics such as electrical characteristics required in a thin film transistor (TFT) even after low temperature firing. do.
  • TFT thin film transistor
  • Zinc oxide (ZnO) has a wide optical bandgap of about 3.3 eV and is a material used for semiconductor manufacturing.
  • Zinc oxide thin films have strong piezoelectric and photoelectric effects, and have similar optical properties to GaN, which is a material of conventional ultraviolet / blue light emitting diode (LED) and laser diode (LD) devices. In particular, it has an excitation binding energy that is three times higher than GaN at room temperature, which enables high-efficiency light emission, and has a very low threshold energy when stimulated spontaneous emission by laser pumping.
  • the zinc oxide thin film has excellent transparency in the infrared and visible light region, electrical conductivity, and durability against plasma, and has a low raw material price, so that thin film transistors (TFTs), doped transparent electrodes, photocatalysts, energy-saving glazing coating materials, Acoustic optical devices, ferroelectric memories, solar cells, reducing gas detection sensors and the like have a wide range of applications.
  • TFTs thin film transistors
  • doped transparent electrodes doped transparent electrodes
  • photocatalysts photocatalysts
  • energy-saving glazing coating materials Acoustic optical devices, ferroelectric memories, solar cells, reducing gas detection sensors and the like have a wide range of applications.
  • Zinc hydroxide is a kind of zinc oxide precursor that is transformed into zinc oxide by firing. Zinc hydroxide is precipitated by dissolving zinc salt in water and adding a basic substance. This method has the advantage of obtaining zinc hydroxide by a simple process, but the basic material used in the process reacts with carbon dioxide in the air to easily form carbonates to generate impurities and precipitate anions in zinc salts together. As a possibility, zinc hydroxide obtained by this method is not suitable for use in oxide semiconductors that require high purity.
  • the present invention has been made in view of the above-described problems, and is intended to provide a method for preparing a zinc oxide precursor for an oxide semiconductor, which is easy to manufacture, has high purity, and is calcinable even at low temperatures, and a zinc oxide precursor and a zinc oxide thin film formed therefrom.
  • dissolving zinc salt in water to obtain a zinc salt solution Adding a basic substance to the zinc salt solution to form a zincate salt solution; And separating the precipitate formed from the zinc salt solution.
  • the zinc salt may be one or a mixture of two or more selected from the group consisting of zinc chloride, zinc sulfate, zinc nitrate, zinc acetate, zinc phosphate, zinc fluoride, zinc bromide, and zinc iodide.
  • the basic substance may be one selected from the group consisting of ammonia water, sodium hydroxide, potassium hydroxide and lithium hydroxide.
  • the basic substance may be added so as to have 5 to 12 moles of hydroxy ions per mole of zinc ions.
  • the basic substance may be a solution portion separated from a supersaturated basic solution.
  • a zinc oxide precursor prepared according to the method described above.
  • a method for producing a zinc oxide thin film comprising the step of heat-treating the zinc oxide precursor at a temperature range of 50 to 200 °C.
  • the heat treatment may be carried out in a temperature range of 100 to 150 °C.
  • the heat treatment may be performed for 1 to 90 minutes.
  • the heat treatment may be performed in air or Ar / H 2 .
  • a method for producing a zinc oxide thin film comprising the step of ultraviolet treatment heat treatment of the zinc oxide precursor at a temperature range of room temperature (25 °C) to 200 °C.
  • the heat treatment may be carried out in a temperature range of room temperature to 150 °C.
  • the heat treatment and ultraviolet treatment may be performed for 1 second to 30 minutes.
  • the ultraviolet light treatment may be performed in the wavelength range of 100 to 1000 nm, which may include visible light.
  • the zinc oxide thin film may be used for a transparent electrode, a solar cell, an optical sensor, a thin film transistor (TFT), zinc oxide nanowires, or a light emitting material.
  • TFT thin film transistor
  • Zinc hydroxide obtained according to the present invention is characterized by high purity and high crystalline structure.
  • the zinc hydroxide obtained in accordance with the present invention can be dissolved in a high solubility to form a zinc oxide precursor solution can be easily applied to the thin film process by the coating method.
  • the zinc oxide precursor solution applied to the substrate by the printing method may form a ZnO thin film having desirable physical properties by low temperature firing, and the ZnO thin film transistor according to an embodiment of the present invention may be further improved by passivation. .
  • the thin film transistor made of the zinc precursor solution may be manufactured to have improved quality and improved device performance within a short processing time.
  • This time reduction in the present invention is not only comparable to the microwave annealing method, but also has a simpler advantage over the microwave annealing method because it is better in saturation field effect mobility and can be adapted to actual industrial use. have.
  • the zinc oxide thin film according to the present invention is widely applicable to various applications such as not only an oxide semiconductor but also a transparent conductive thin film and a gas sensor.
  • Example 1 is a graph showing the results of TGA (Thermogravimetric Analysis) thermal analysis of zinc hydroxide obtained in Example 1-1.
  • Figure 2 is a photograph taken with zinc hydroxide obtained in Example 1-1 with a Field Emission Scanning Electron Microscope (FE-SEM).
  • FE-SEM Field Emission Scanning Electron Microscope
  • Figure 3a is an X-ray diffraction (XRD) graph (black) of zinc hydroxide obtained in Example 1-1
  • Figure 3b is an XRD graph (black) of zinc oxide obtained in Example 2-1
  • the gray graph in the field is for zinc hydroxide standard.
  • Example 4 is an XRD graph of the zinc hydroxide obtained in Example 1-1 after heat treatment at 100 ° C. for 1 hour or 3 hours.
  • Example 5 is an XRD graph of the zinc hydroxide obtained in Example 1-1 after treatment with different annealing times at 150 ° C.
  • 6a is a photograph of a solution in which zinc hydroxide prepared according to Example 1-1 was dissolved in 25% ammonia water, 1% by weight, 2% by weight, 3% by weight, 4% by weight, and 5% from left to right, respectively. Solution by weight concentration.
  • Figure 6b is a photograph for comparison with Figure 6a, shows the result of dissolving zinc hydroxide of Junsei in 25% ammonia water. From the left, a picture of 0.9% by weight and 1.2% by weight of the solution is shown and the maximum solubility is about 0.9%, showing a solubility lower than that shown in Figure 6a.
  • Example 7 is a photograph of a solution obtained by dissolving zinc oxide obtained in Example 2-1 at 150 ° C. for 3 minutes and then dissolved in 25% ammonia water, and 0.45% by weight, 0.90% by weight, and 1.35% by weight from left to right, respectively. %, 1.8% by weight solution.
  • FIG. 8 is a photograph of a solution in which commercially available zinc oxide is heat-treated at 150 ° C. for 3 minutes and then dissolved in 25% ammonia water.
  • the solution is 0.45% by weight, 0.90% by weight, and 1.35% by weight, respectively, from left to right.
  • 9A and 9B show the output curves and the transfer curves of transistors using Zn (OH) 2 and ZnO thin films obtained in this example using various conditions, respectively.
  • 10A to 10D are FE-SEMs of ZnO thin films obtained in Examples 2-1, 2-2, 2-3, and 2-6, and the thin film thicknesses are described in each of the images.
  • Example 11 is a graph showing an X-ray diffraction pattern of the ZnO thin film obtained in Example 2-1 and a graph (B) showing an X-ray diffraction pattern of the ZnO thin film obtained in each of Examples 2-3. .
  • 12A to 12C are graphs showing XPS spectra of the ZnO thin films obtained in Examples 2-1, 2-3, and 2-6.
  • dissolving zinc salt in water to obtain a zinc salt solution Adding a basic substance to the zinc salt solution to form a zincate salt solution; And separating the precipitate formed from the zinc salt solution.
  • a method for preparing a zinc oxide precursor which method is based on the following Scheme 1.
  • the zinc hydroxide thus obtained is in a pure state with almost no impurities, and may be pyrolyzed at a low temperature of 50 to 200 ° C., more preferably 100 to 150 ° C., to be changed to zinc oxide.
  • the heat treatment represents an embodiment performed without ultraviolet irradiation, the heat treatment time may be 1 minute to 90 minutes.
  • Embodiments in which the heat treatment is carried out simultaneously with ultraviolet irradiation are described below, and the zinc oxide precursor firing can be made in a shorter time at a lower temperature than the method of firing only by heat treatment.
  • Zinc containing zinc that can be used in the present invention are water-soluble zinc salts.
  • Non-limiting examples of zinc salts that can be used in the present invention include zinc nitrate, zinc chloride, zinc acetate, zinc sulfate, zinc phosphate, zinc fluoride, zinc bromide, zinc iodide, and the like, or may be used by mixing one or two or more of them.
  • zinc salts zinc nitrate is preferred in view of thermal decomposition by low temperature firing.
  • the basic material usable in the present invention various basic materials which can be easily dissolved in water to form a basic solution may be used. Examples thereof include NaOH, KOH, LiOH, ammonia water, but are not limited thereto.
  • the basic material reacts with carbon dioxide in the air to easily form carbonate
  • the basic material in order to prevent the formation of carbonate, is supersaturated in water and separated from the solution part by focusing on the low water solubility of the carbonate. Can be used. This can minimize the incorporation of unnecessary carbonates into zinc hydroxide. In this way, the formation of zinc carbonate can also be prevented.
  • the basic substance is used in excess with respect to zinc ions. Specifically, more than theoretical hydroxy ions 5 per mol of zinc ions To 12 Basic materials are used to molar. If used less than 5 moles, the formation of ginkects is not easy and The use of more than mole is insignificant because it inhibits the formation of zinc hydroxide in proportion to it.
  • the temperature and pressure conditions of the reaction is not particularly limited as long as it meets the object of the present invention, can be carried out at room temperature and atmospheric pressure and can be heated to a temperature of 50 °C or less to increase the reaction rate, but at higher temperatures Zinc oxide may be formed.
  • the zinc hydroxide obtained by the above reaction is separated, washed and dried by conventional methods in the art.
  • Zinc hydroxide is added to distilled water, C 1 -C 3 alcohol, ammonia or a mixture thereof to form a zinc oxide precursor solution.
  • Zinc hydroxide is doped with one or more metals selected from the group consisting of aluminum (Al), tin (Sn), indium (In), gallium (Ga), iron (Fe), antimony (Sb), and lithium (Li) ( doping).
  • a doped metal may be added to the zinc oxide precursor solution in which zinc hydroxide is dissolved.
  • the zinc concentration in the zinc oxide precursor solution is preferably 0.1 to 5% by weight, but is not necessarily limited thereto.
  • concentration is lower than 0.1% by weight, the thickness of the zinc oxide thin film to be formed cannot be easily adjusted, and when higher than 5% by weight, it is difficult to obtain a transparent and uniform precursor solution.
  • the zinc oxide precursor solution of the present invention may contain no or less stabilizer or modifier because of its high solubility in solvents. Since the zinc oxide precursor through the conventional synthesis method has a low solubility in solvents, the solution can be made in a limited range (0.9% or less), but according to the present invention, even without adding a stabilizer or a modifier or a small amount, Clear and homogeneous zinc hydroxide precursor solutions can be prepared.
  • stabilizers include, but are not limited to, amine stabilizers such as monoethanolamine, diethanolamine, and triethanolamine. However, the condition of not adding a stabilizer is best because of the specificity of the semiconductor precursor.
  • the concentration in the precursor solution for zinc oxide thin film is controlled according to the zinc concentration in the precursor solution for zinc oxide thin film, but may be accompanied by a deterioration after the formation of the semiconductor, so it is preferably included 5 wt% or less based on 100 parts by weight of zinc. .
  • the coating method of the zinc oxide precursor solution on the substrate is spin coating, dip coating, roll coating, screen coating, spray coating, spin casting ( spin casting, flow coating, screen printing, ink jet, drop casting, and the like, but are not necessarily limited thereto.
  • the substrate to which the zinc oxide precursor solution is coated may be at least one selected from the group consisting of a wafer substrate, an ITO substrate, a quartz glass substrate, and a plastic substrate, but is not limited thereto.
  • the purity of the compound and the homogeneous and dense morphology of the formed thin film play a particularly important role in high performance semiconductor thin films.
  • the influence of grain morphology and thin film density on the operational parameters of the thin film transistor is a main factor due to the grain boundary effect.
  • the morphology of the coated surface should be as dense as possible at low temperature processed device performance.
  • porous agglomeration is generated on the surface of the thin film, which is the main interface state in the low temperature firing method, which not only restricts carrier mobility but also subthreshold slope and off current.
  • switching voltage switching voltage
  • a zinc oxide thin film can be formed in a short time by simultaneously treating the solution containing zinc hydroxide with heat and ultraviolet rays at 50 to 200 ° C, more preferably at 100 to 150 ° C or lower.
  • Ultraviolet treatment can be performed in the wavelength range of 100-1000 nm which may contain visible light, More preferably, it is 180-400 nm wavelength range. Rapid dehydration kinetics can occur during ultraviolet and heat treatment, followed by condensation of Zn-O-Zn bonds. At relatively low temperatures, the crystallization process is difficult mechanically and the rearrangement of Zn-O-Zn bonds is hindered.
  • Another aspect of the invention relates to an electronic component comprising a zinc oxide thin film obtained by the method according to one aspect of the invention.
  • electronic components include, but are not necessarily limited to, transparent electrodes, solar cells, optical sensors, TFTs, zinc oxide nanowires, and light emitting materials.
  • NaOH sodium hydroxide
  • KHP potassium hydrogen phthalate
  • An aqueous zinc solution was prepared by dissolving 49.8 g of zinc nitrate hexahydrate in a 5 L two-necked round flask in 900 ml of tertiary distilled water. 600 ml of a 2.4 M NaOH solution without carbonate was added to the aqueous zinc solution. The solution was slowly heated and stirred at 50 ° C. for 2 hours. Particles were formed while Zn (OH) 2 was formed during stirring heating. The produced Zn (OH) 2 was filtered under reduced pressure using a paper filter, and the filtered material was again dispersed in distilled water and washed. In the last step, the mixture was washed with methanol and dried naturally to obtain zinc hydroxide.
  • Example 1-1 In the method of Example 1-1, the heating temperature was lowered to 40 ° C. and the stirring time was about 3 hours to obtain desired zinc hydroxide.
  • Example 1-1 In the method of Example 1-1, the heating temperature was lowered to 25 ° C. and the stirring time was about 10 hours to obtain desired zinc hydroxide.
  • Example 1-1 In the method of Example 1-1, the desired heating temperature was lowered to 15 ° C. and stirring time was about 24 hours to obtain desired zinc hydroxide.
  • the desired zinc hydroxide was obtained in the same manner using zinc chloride instead of zinc nitrate in Example 1-1.
  • Example 1-1 zinc zinc was used instead of zinc nitrate to obtain desired zinc hydroxide in the same manner.
  • Example 1-1 desired zinc hydroxide was obtained in the same manner using potassium hydroxide instead of sodium hydroxide.
  • Example 1-2 desired zinc hydroxide was obtained in the same manner using potassium hydroxide instead of sodium hydroxide.
  • Example 1-1 to 1-6 desired zinc hydroxide was obtained in the same manner using 25% ammonia water instead of sodium hydroxide.
  • Zinc hydroxide (Zn (OH) 2 ) synthesized above was dissolved in aqueous NH 4 OH (Duksan, 25-30%) to prepare a 2% by weight precursor stock solution to prepare a ZnO layer.
  • the Zn (OH) 2 / NH 4 OH solution was filtered through a 0.2 ⁇ m PVDF filter and spin coated at 4000 rpm for 30 seconds on a 100 nm SiO 2 / p-doped Si substrate.
  • the coated thin film was baked to cure for 1 hour on a hot plate preheated to 150 ° C. in air.
  • a source and drain electrode was fabricated by depositing an aluminum layer on the ZnO thin film using a metal evaporator (VPC-260) having a 50 ⁇ m channel width and 40 ⁇ m length to produce a bottom-gate in the fabrication of a ZnO base thin film transistor. And top-contact thin film transistor structures.
  • VPC-260 metal evaporator
  • a zinc oxide thin film and a device were manufactured in the same manner as in Example 2-1, except that Ar / H 2 was used instead of air as the firing condition. More specifically, the coated thin film was cured at 150 ° C. while flowing Ar / H 2 at 100 cc / min in a tube furnace.
  • a zinc oxide thin film and a device were manufactured in the same manner as in Example 2-1, except that 150 ° C. heat treatment / ultraviolet light exposure was simultaneously performed in air under firing conditions.
  • a 1.1 kW medium pressure mercury UV lamp (Lichtzen, South Korea) with peak intensity at 365 nm was used and the distance from the sample to the lamp was set to 7 cm.
  • the surface temperature of the hot plate increased to 10 ° C. and then settled to the desired temperature within 5 minutes.
  • a zinc oxide thin film and a device were manufactured in the same manner as in Example 2-3, except that the zinc hydroxide coating was performed twice.
  • Example 2-3 and Al 2 O 3 gate insulator having a thickness of 100 nm were further coated by atomic layer deposition. In the same manner, zinc oxide thin films and devices were prepared.
  • a zinc oxide thin film and a device were manufactured in the same manner as in Example 2-3, except that 4 wt% zinc hydroxide solution was used.
  • Zinc oxide thin film by the method described in Example 2-3 except for using a 4% by weight zinc hydroxide solution, and proceeding to the process described in Example 2-1 to the process described in Example 2-3 And devices.
  • Thermogravimetric analysis of Zn (OH) 2 powder was carried out at 2 ° C./min heat treatment rate using a TA instrument (Q50).
  • FT-IR Fourier transform infrared spectroscopy
  • the relative oxygen vacancies in the ZnO thin films were confirmed using X-ray photoelectron spectroscopy (XPS).
  • the electrical characteristics of the device were analyzed in ambient air using a semiconductor parameter analyzer (Agilent 4155B).
  • Example 1-1 The result of heat-treating the zinc hydroxide obtained in Example 1-1 is shown in FIG. Referring to Figure 1, the zinc hydroxide obtained in Example 1-1 was changed to zinc oxide in one step at 130 °C. In this process, as shown in the following reaction formula 2, one of the water powders from the white powder Zn (OH) 2 exits and decomposes into ZnO. That's about 81.88%:
  • Example 1-1 The zinc hydroxide obtained in Example 1-1 was photographed by FE-SEM and shown in FIG. 2. Referring to FIG. 2, the zinc hydroxide obtained in Example 1-1 was obtained cleanly as crystals of one form.
  • Example 1-1 XRD of the zinc hydroxide obtained in Example 1-1 was measured, and the result is shown in FIG. 3A.
  • the XRD (black graph) of zinc hydroxide obtained in Example 1-1 is consistent with the standard sample (gray graph) of zinc hydroxide having an orthorhomic structure, and the oxidation obtained in Example 2-1 according to FIG. 3B.
  • the XRD graph of zinc (black graph) is consistent with the standard sample of zinc oxide (grey graph).
  • Example 1-1 After the zinc hydroxide obtained in Example 1-1 was heat-treated at 100 ° C. for 1 hour or 3 hours, respectively, the XRD was measured and the graph is shown in FIG. 4. From the fact that XRD after heat treatment for 1 hour and 3 hours was almost identical, it was found that the zinc hydroxide obtained in Example 1-1 changed to zinc oxide even with a short time firing within 100 hours at 100 ° C.
  • Example 1-1 After firing the zinc hydroxide obtained in Example 1-1 at 150 ° C. for 1 minute, 3 minutes, 5 minutes, and 15 minutes, the FT-IR was measured for each, and the graph is shown in FIG. 5.
  • Example 1-1 The zinc hydroxide obtained in Example 1-1 was dissolved in 25% aqueous ammonia at 1% by weight, 2% by weight, 3% by weight, 4% by weight and 5% by weight, respectively, and photographed.
  • Example 1-1 the zinc hydroxide obtained in Example 1-1 was found to be completely transparent and homogeneously dissolved to form a solution even when dissolved in 25% ammonia water at a concentration of 5% by weight.
  • Zinc oxide obtained in Example 1-1 was calcined at 150 ° C. for 3 hours to dissolve zinc oxide formed in 25% ammonia water at a concentration of 0.45% by weight, 0.90% by weight, 1.35% by weight, and 1.8% by weight. 7 is shown.
  • the zinc oxide was completely dissolved in ammonia water even at a concentration of 1.35 wt%.
  • the zinc hydroxide synthesized in Example 1-1 was dissolved in 25% ammonia water to prepare a zinc oxide precursor solution having a concentration of 1% by weight, 2% by weight, 3% by weight, 4% by weight, and 5% by weight, respectively.
  • the thickness change of the zinc oxide thin film obtained after spin coating the prepared zinc oxide precursor solution on a silicon wafer substrate and sufficiently baked at 150 ° C. was investigated using FE-SEM. As a result, the thickness of the zinc oxide thin film was found to vary almost linearly with the zinc oxide precursor concentration.
  • FIGS. 10A-10D FE-SEM images of ZnO thin films prepared from the synthesized Zn (OH) 2 solution using various firing conditions are shown in FIGS. 10A-10D.
  • Example 2-1 The thin film was 35.5 nm thick (FIG. 10A), similar to the thin film thickness (33.7 nm) of FIG. 10C, which was simultaneously treated with UV and heat for 3 minutes.
  • the size of grain boundaries in thin films is determined by firing methods such as ultraviolet or heat treatment.
  • the grain boundaries of the UV treated thin film (FIGS. 10B and 10C) were larger than the thin film grain boundaries (FIG. 10A) by heat treatment without UV treatment.
  • Example 2-6 thin film has a larger grain than the Example 2-1 thin film (Example 10a) and uses a Zn (OH) 2 solution at a concentration of at least 2 to 3 times higher than other samples. It had a thin film thickness of 48.5 nm thicker even though the coating was made once.
  • Example 1-1 The amount of impurities present in the zinc hydroxide obtained in Example 1-1 was investigated by using ICP-MS. If the purity of the starting material is more than 99.50%, all impurities of other cations contained are negligible below ppm. Therefore, the purity of the zinc hydroxide produced in Example 1-1 is very excellent.
  • Example 1-1 The zinc hydroxide obtained in Example 1-1 was dissolved in 25% ammonia water to prepare a zinc oxide precursor solution at a concentration of 2% by weight. The solution was spin coated onto a p-doped silicon wafer made of 100 nm silicon oxide and then calcined to 110 ° C. After that, the source and drain electrodes were formed by depositing aluminum, and then TFT electrical characteristics were measured. The results are summarized in Table 3 below, and the transfer curve of the oxide semiconductor is shown in FIG. 9B:
  • Table 3 shows the importance of thin film transistors such as field-effect mobility, subthreshold swing, I on / I off ratio and threshold voltage (V th ) using various firing conditions. The electrical characteristics are summarized.
  • the zinc oxide thin film of Example 2-3 exhibited substantially similar electrical characteristics to the zinc oxide thin film of Example 2-1, which is different from ZnO grain (when UV irradiation and heat treatment are performed simultaneously). This means that the semiconductor channel in grains can be effectively activated even at shorter process times.
  • Example 2-4 In the zinc oxide thin film of Example 2-4, as a result of coating the same solution twice, the channel thickness was increased to improve the mobility performance twice.
  • ZnO thin-film transistors fabricated with patterned gates were modified to meet 100 nm thick Al 2 O 3 by UV irradiation at 150 ° C. for 3 minutes and atomic layer deposition (ALD) into the gate dielectric. Improved.
  • the transfer characteristics of the ZnO-TFTs of Examples 2-5 exhibited a low off-current of less than 10 ⁇ 12 A and a higher on-off current ratio of about 10 7 (see FIG. 9B).
  • the measured saturation mobility was 1.15 cm 2 / Vs at 40V gate voltage, and the threshold voltage (V th ) and subcritical swing were 25V and 0.6V / dec, respectively.
  • the zinc oxide thin films of Examples 2-6 and 2-7 show typical field effect transistor embodiments according to FIG. 9B.
  • the I on / I off current ratio is about 10 6 and is expected to be further improved by the patterned active channel layer.
  • Threshold voltage (V th ) and subthreshold swing were 14.6 V and 0.47 V / dec, respectively.
  • the field effect mobility extracted from the saturation regime was 2.91 cm 2 / Vs at the gate voltage of 40V when irradiated with UV light at 150 ° C for 3 minutes.
  • the electrical properties of the thin film transistor are also affected by the thickness and grain size of the ZnO thin film.
  • the zinc oxide thin film of Example 2-6 has an improved field effect mobility of 2.91 cm 2 / Vs because of the large grain boundary and the thin film thickness. Indicated. Larger ZnO crystals due to simultaneous UV / heat treatment significantly improve the mobility of the ZnO thin film transistor because the migration length is reduced throughout the grain boundaries.
  • the graph of FIG. 11 shows the X-ray diffraction pattern (A curve) of the ZnO thin film heat-treated at 150 ° C. without UV treatment and the X-ray diffraction pattern (B curve) of the ZnO thin film heat-treated at 150 ° C. for 3 minutes under UV irradiation. .
  • the A curve does not show a ZnO diffraction pattern
  • the B curve is based on three diffraction peaks of polycrystalline ZnO in the (100), (002), and (101) planes as shown in FIG. Represents a pattern. It was proved that the ZnO thin film annealed under UV treatment exhibited an increased XRD pattern than the ZnO thin film annealed without UV treatment. That is, UV / thermal co-treatment increases both the deposition of the zinc precursor and the thin film crystallization and greatly reduces the overall process time.
  • FIGS. 12A-12C Another important point in the properties of oxide semiconductor materials is the bulk defect structure, and the general trend of the relative concentration of the internal ZnO thin film can be confirmed by XPS.
  • the O 1s XPS spectrum of the ZnO thin film is shown in FIGS. 12A-12C, which are determined by the firing method.
  • the zinc hydroxide thin film obtained in the present invention was converted to ZnO by heat treatment at 150 ° C. for 1 hour (see FIG. 12A).
  • These peaks represent lattice oxygen, oxygen near the oxygen vacancies and hydroxy oxygen, respectively.
  • oxygen vacancies and hydroxy peaks generated during the firing process throughout the condensation and dehydration processes, but all three XPS results appear to be very similar.
  • the oxygen vacancies are the source of charge carriers, while the hydroxy moiety slightly degrades device mobility.
  • Zn-OH-Zn is easily converted to Zn-O-Zn, and surface hydroxy groups are removed to influence other factors such as grain size and crystallinity as shown in Examples 2-6.
  • the overall mobility then increased.
  • the zinc hydroxide prepared in the present invention can be dissolved in a solvent at a high concentration, so it can be expected to make an oxide semiconductor in the printing process in the future, and in particular, it can be used as a backplane semiconductor by being changed to zinc oxide at low temperature. It is expected to contribute to the industry or the sensor industry.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Thin Film Transistor (AREA)

Abstract

La présente invention concerne un procédé pour fabriquer des cristaux de haute pureté d'hydroxyde de zinc, qui est un précurseur d'oxyde de zinc utilisé pour des semi-conducteurs d'oxyde, et un procédé pour fabriquer un dispositif à transistor à couche mince de ZnO qui est revêtu à la tournette en utilisant l'hydroxyde de zinc fabriqué par celui-ci.
PCT/KR2014/002337 2013-03-20 2014-03-20 Procédé pour fabriquer un précurseur d'oxyde de zinc, précurseur d'oxyde de zinc obtenu par celui-ci, et couche mince d'oxyde de zinc Ceased WO2014148830A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2013-0029569 2013-03-20
KR20130029569 2013-03-20
KR1020130164867A KR101567809B1 (ko) 2013-03-20 2013-12-27 산화아연 전구체의 제조방법, 이로부터 수득되는 산화아연 전구체 및 산화아연 박막
KR10-2013-0164867 2013-12-27

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WO2014148830A1 true WO2014148830A1 (fr) 2014-09-25

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CN107221552A (zh) * 2017-05-25 2017-09-29 深圳市华星光电技术有限公司 Toc型oled显示器的制作方法及toc型oled显示器
CN112456541A (zh) * 2020-12-22 2021-03-09 南京航空航天大学 一种提高氧化锌材料辐照稳定性的方法
WO2022143833A1 (fr) * 2020-12-31 2022-07-07 Tcl科技集团股份有限公司 Procédé de régulation de la mobilité d'électrons d'oxyde de zinc

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US20060289024A1 (en) * 2005-03-11 2006-12-28 Philip Morris Usa Inc. Catalysts for low temperature oxidation of carbon monoxide
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KR100936281B1 (ko) * 2009-08-25 2010-01-13 한국지질자원연구원 ＺｎＯ 나노입자의 제조방법 및 이를 이용한 ＺｎＯ 나노유체의 제조방법

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107221552A (zh) * 2017-05-25 2017-09-29 深圳市华星光电技术有限公司 Toc型oled显示器的制作方法及toc型oled显示器
CN112456541A (zh) * 2020-12-22 2021-03-09 南京航空航天大学 一种提高氧化锌材料辐照稳定性的方法
WO2022143833A1 (fr) * 2020-12-31 2022-07-07 Tcl科技集团股份有限公司 Procédé de régulation de la mobilité d'électrons d'oxyde de zinc

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