KR101913757B1 - Method for preparing tungsten oxide - Google Patents

Method for preparing tungsten oxide Download PDF

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KR101913757B1
KR101913757B1 KR1020150056046A KR20150056046A KR101913757B1 KR 101913757 B1 KR101913757 B1 KR 101913757B1 KR 1020150056046 A KR1020150056046 A KR 1020150056046A KR 20150056046 A KR20150056046 A KR 20150056046A KR 101913757 B1 KR101913757 B1 KR 101913757B1
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deposition
temperature
tungsten oxide
heat treatment
minutes
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KR1020150056046A
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Korean (ko)
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KR20160125184A (en
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손세희
채병준
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주식회사 엘지화학
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G41/00—Compounds of tungsten
    • C01G41/02—Oxides; Hydroxides

Abstract

The present application relates to a method for producing tungsten oxide. In this application, it is possible to provide a method capable of producing tungsten oxide having excellent physical properties through a low-temperature process.

Description

TECHNICAL FIELD The present invention relates to a method for preparing tungsten oxide,

The present application relates to a method for producing tungsten oxide.

BACKGROUND ART [0002] Transition metal oxides such as tungsten oxide have been studied extensively due to their unique physical and chemical properties. For example, a non-fully oxidized tungsten oxide (WO 3 -x ) can be used for a wide variety of applications, including field emission, gas sensing, electrochromic, And has attracted much attention due to its novel and various properties such as photocatalytic properties.

Chemical Vapor Deposition (CVD), laser ablation, or template method are known to be commonly used for the production of transition metal oxides such as tungsten oxide and tungsten oxide. However, all of the above methods are high temperature processes requiring a high temperature of about 1000 DEG C or more, and there is a limitation in the selection and application of deposition substrates.

It is an object of the present invention to provide a method for producing tungsten oxide and a method for manufacturing tungsten oxide having excellent physical properties through a low temperature process in one aspect.

An exemplary method of making the present application may include a deposition step of forming a layer of tungsten oxide or a precursor thereof on a substrate and a heat treatment step of heat-treating the deposited deposition material.

The deposition and / or heat treatment step may be performed to satisfy any one of the following formulas (1) and (2).

[Equation 1]

T1 / M ≤ 6 ° C / min

[Equation 2]

T2 / M ≥ 24 ℃ / min

T1 is the temperature at which the organic tungsten compound is held in the deposition step, T2 is the heat treatment temperature in the heat treatment step, and M is the time for depositing the tungsten oxide or organic tungsten compound on the substrate in the deposition step.

T1 / M in equation (1) can be 1 deg. C / min or more or 2 deg. C / min or more in other examples.

T2 / M in Equation 2 may be 40 deg. C / min or less, 35 deg. C / min or less, 30 deg. C / min or 28 deg. C / min or less in other examples.

When the vapor deposition and / or the heat treatment step is carried out so as to satisfy the formula (1) or (2), it is possible to provide a method for producing tungsten oxide having excellent physical properties through a low temperature process.

The progress of the specific process satisfying the formula 1 or 2 will be described below.

The deposition step may include, for example, depositing tungsten oxide or the compound on the substrate while maintaining the organic tungsten compound having a melting point of 300 DEG C or lower at a temperature in the range of 100 DEG C to 400 DEG C .

In the method of the present application, by using an organic tungsten compound having a low melting point as an evaporation source, tungsten oxide of excellent quality can be produced by a low-temperature process. The melting point of the organic tungsten compound used as an evaporation source may be 100 deg. C or higher, 120 deg. C or higher, 140 deg. C or higher, or 160 deg. C or higher in another example. In another example, the melting point of the organic tungsten compound used as the evaporation source may be about 290 ° C or lower, about 280 ° C or lower, about 270 ° C or lower, about 260 ° C or lower, about 250 ° C or lower, about 240 ° C or lower, About 220 캜 or less, about 210 캜 or less, about 200 캜 or less, about 190 캜 or less, or about 180 캜 or less.

The kind of the organic tungsten compound as the deposition source is not particularly limited as long as it has the above melting point. For example, W (CO) 6 or W (OC 6 H 5 ) 6 can be used as the organic tungsten compound, but the present invention is not limited thereto.

The deposition step may include maintaining the organic tungsten compound as described above at a temperature in the range of about 100 캜 to about 400 캜 to form deposits of tungsten oxide or the compound on the substrate. The temperature at which the organic tungsten compound is maintained may be 150 ° C or higher, 200 ° C or higher, or 250 ° C or higher in another example. In another example, the temperature may be about 350 ° C or less, 340 ° C or less, 330 ° C or less, 320 ° C or less, or 310 ° C or less. The target tungsten oxide can be effectively produced when the temperature is controlled at a level satisfying the formula 1 or 2 and within the above range.

A method for depositing tungsten oxide or its precursor as a deposition material on a substrate under the above temperature is not particularly limited and a known method can be applied.

FIG. 1 is a view schematically showing a process of forming an evaporation material on a substrate 20 using the organic tungsten compound 10.

As shown in FIG. 1, the deposition process may be performed, for example, in a deposition apparatus such as a crucible. The crucible may be made of, for example, aluminum. The deposition apparatus may include a heat source 40 to maintain the temperature of the organic tungsten compound 10 within the above-mentioned range. The temperature of the organic tungsten compound (10) as a deposition source can be maintained in the above-described range through the heat source (40).

When the temperature of the organic tungsten compound as a deposition source is maintained in the above-described range through the heat source, a vaporized evaporation source can be deposited on the substrate 20. The evaporation source may be deposited in the form of tungsten oxide while being deposited on the substrate, or the organic tungsten compound itself may be deposited on the substrate.

The kind of the substrate 20 on which the deposition material is formed is not particularly limited, and a suitable substrate may be applied according to the intended use. According to the method of the present application, deposition at a low temperature is possible, and the degree of freedom of substrate selection can also be maximized. As the substrate, a silicon (Si) based substrate can be exemplified, but the present invention is not limited thereto.

The deposition time in the deposition step may be determined according to the shape or thickness of the desired tungsten oxide. For example, the deposition time can be appropriately adjusted within a range of 10 minutes to 180 minutes. The deposition time may be 20 minutes or more, 30 minutes or more, 40 minutes or 50 minutes or more in another example. Also, the deposition time may be less than 150 minutes, less than 120 minutes, less than 110 minutes, less than 100 minutes, less than 90 minutes, less than 80 minutes, or less than 70 minutes in other examples. The desired tungsten oxide can be effectively produced when the deposition time satisfies the formula 1 or 2 and is adjusted at a level within the above range.

The thickness of the deposition material deposited in the deposition step in the above manner is not particularly limited and may be adjusted within a range of, for example, about 30 nm to 2000 nm.

The temperature of the substrate can be adjusted for effective deposition. For example, the temperature of the substrate can be adjusted so that the absolute value of the difference from the holding temperature of the organic tungsten compound in the deposition process falls within a range of about 175 캜 to 275 캜. In this range, the temperature of the substrate can be adjusted to a lower range than the holding temperature of the organic tungsten compound.

The manufacturing method of the present application may include, for example, a step of heat-treating the deposited material after the deposition step. The heat treatment process may be performed by a so-called RTA (Rapid Thermal Annealing) method. The crystallinity of the deposition material can be increased by this method.

The heat treatment step may include, for example, heating the deposition material to a temperature in the range of 600 占 폚 to 900 占 폚. In one example, the heating in the heat treatment step may be performed for about 1 to 5 minutes. The heat treatment temperature may be, for example, 650 ° C or higher, 700 ° C or higher, or 750 ° C or higher. In addition, the heat treatment temperature may be about 850 DEG C or lower in another example. The desired tungsten oxide can be effectively produced when the heat treatment temperature satisfies the equation (2) and is adjusted at a level within the above range.

In the above example, the heat treatment time may be about 4 minutes or less, about 3 minutes or less, or about 150 seconds or less in other examples.

Through the heat treatment in this range, tungsten oxide having an appropriate level of crystallinity can be formed.

The heat treatment may be performed in an oxygen atmosphere. For example, the heat treatment can be performed while injecting oxygen gas at a flow rate of about 1 to 10 sccm. The flow rate of the oxygen gas may be about 2 sccm or more, 3 sccm or more, or 4 sccm or more in another example. In another example, the flow rate of the oxygen gas may be about 9 sccm or less, 8 sccm or less, 7 sccm or less, or 6 sccm or less. When a heat treatment process is performed in this range, an appropriate tungsten oxide can be produced.

The tungsten oxide produced in the present application may be crystalline tungsten oxide. The term crystallinity in the present application may mean the case of having a crystalline peak defined in the JCPDS card at the time of analysis by X-ray diffraction (XRD). The JCPDS card number applied for the determination of the crystal structure is known as follows.

<Type of JCPDS card>

Monoclinic: 43-1035

Triclinic: 20-1323 or 32-1395

Cubic: 41-0905

Tetragonal: 05-0388

Hexagonal: 33-1387

The tungsten oxide produced in the present application may be tungsten oxide containing at least monoclinic or triangular crystal structure among the crystal structures. At this time, the fact that tungsten oxide includes the crystal structure can mean that at least one of the peaks identified in the XRD analysis is a peak corresponding to the crystal structure. For example, the main peak of the XRD peak corresponds to the crystal structure. In the above, the term main peak may mean the peak having the highest intensity among the peaks identified in the XRD peak.

The tungsten oxide thus produced has an appropriate crystal structure and exhibits various physical properties suitable for various applications and can be effectively used in various applications.

In this application, it is possible to provide a method capable of producing tungsten oxide having excellent physical properties through a low-temperature process.

FIG. 1 is a diagram illustrating an exemplary process of the method of the present application.
Figures 2 to 4 show the structure of the tungsten oxide particles produced in the examples of the present application.

Hereinafter, the manufacturing method and the like of the present application will be described in detail through examples and comparative examples, but the scope of the present application is not limited to the following examples.

One. XRD  Determination of crystallinity and crystal structure by measurement

XRD analysis was performed on the area of 2? From 20 to 40 degrees (based on Cu measurement K?) Using the Bragg-Brentano method using a Bruker D4 Endeavor instrument. The measured diffraction pattern was compared with a known pattern of tungsten oxide on JCPDS to confirm the crystal structure.

Example  One.

As shown in FIG. 1, tungsten oxide was produced using a deposition apparatus formed by a crucible 30 made of aluminum. As the heat source 40, a hot plate was used. A tungsten carbonyl (W (CO) 6 ) powder as an organic tungsten compound was placed in the apparatus and deposition was performed for about 1 hour while the temperature of the heat source 40 was maintained at about 300 ° C., ). &Lt; / RTI &gt; Thereafter, RTA (rapid thermal annealing) was performed at a temperature of about 700 캜 for about 2 minutes while introducing oxygen gas at a flow rate of about 5 sccm to prepare crystalline tungsten oxide particles. TEM photographs of the produced particles are summarized in Fig.

Example  2.

While the temperature of the heat source 40 is maintained at about 300 DEG C, the deposition is performed for about 30 minutes to form a deposit on the substrate 20. While oxygen gas is injected at a flow rate of about 5 sccm, Crystalline titanium oxide particles were prepared in the same manner as in Example 1 except that RTA (rapid thermal annealing) was performed at a temperature of about 2 minutes. Photographs of the produced particles are summarized in Fig.

Example  3.

While the temperature of the heat source 40 is maintained at about 300 DEG C, the deposition is performed for about 1 hour to form a deposit on the substrate 20. While oxygen gas is injected at a flow rate of about 5 sccm, Crystalline titanium oxide particles were prepared in the same manner as in Example 1 except that RTA (rapid thermal annealing) was performed at a temperature of about 2 minutes. A photograph of the particles produced is summarized in Fig.

Example  4.

While the temperature of the heat source 40 is maintained at about 300 DEG C, the deposition is performed for about 2 hours to form a deposit on the substrate 20. While oxygen gas is injected at a flow rate of about 5 sccm, Crystalline titanium oxide particles were prepared in the same manner as in Example 1 except that RTA (rapid thermal annealing) was performed at a temperature of about 2 minutes.

Example  5.

While the temperature of the heat source 40 is maintained at about 200 DEG C, the deposition is performed for about one hour to form a deposition material on the substrate 20. While oxygen gas is injected at a flow rate of about 5 sccm, Titanium oxide particles were prepared in the same manner as in Example 1 except that RTA (rapid thermal annealing) was performed at a temperature of about 2 minutes.

Example  6.

While the temperature of the heat source 40 is maintained at about 300 DEG C, the deposition is performed for about 2 hours to form a deposition material on the substrate 20. While oxygen gas is injected at a flow rate of about 5 sccm, Titanium oxide particles were prepared in the same manner as in Example 1 except that RTA (rapid thermal annealing) was performed at a temperature of about 2 minutes.

Example  7.

While the temperature of the heat source 40 is maintained at about 200 DEG C, the deposition is performed for about one hour to form a deposit on the substrate 20. While oxygen gas is injected at a flow rate of about 5 sccm, Titanium oxide particles were prepared in the same manner as in Example 1 except that RTA (rapid thermal annealing) was performed at a temperature of about 2 minutes.

Comparative Example  One.

While the temperature of the heat source 40 is maintained at about 200 DEG C, the deposition is performed for about 30 minutes to form a deposit on the substrate 20. While oxygen gas is injected at a flow rate of about 5 sccm, Titanium oxide particles were prepared in the same manner as in Example 1 except that RTA (rapid thermal annealing) was performed at a temperature of about 2 minutes.

Comparative Example  2.

The deposition material is formed on the substrate 20 by performing the deposition for about 30 minutes while the temperature of the heat source 40 is maintained at about 300 DEG C and oxygen gas is introduced at a flow rate of about 5 sccm, Titanium oxide particles were prepared in the same manner as in Example 1 except that RTA (rapid thermal annealing) was performed at a temperature of about 2 minutes.

Comparative Example  3.

While the temperature of the heat source 40 is maintained at about 200 DEG C, deposition is performed for about 30 minutes to form a deposit on the substrate 20, and oxygen gas is introduced at a flow rate of about 5 sccm, Titanium oxide particles were prepared in the same manner as in Example 1 except that RTA (rapid thermal annealing) was performed at a temperature of about 2 minutes.

The results of the above Examples and Comparative Examples are summarized in Table 1 below.

Example Comparative Example One 2 3 4 5 6 7 One 2 3 Crystallinity A A A A B B B C C C Crystal structure WO 3 WO 3 WO 3 WO 3 WO 3 like WO 3 like WO 3 like - - -

In Table 1, A is a case where a peak due to a monoclinic crystal and / or a triangular crystal structure is strongly observed, and B is a case where a peak due to the monoclinic crystal and / or triple crystal structure is weakly observed, C is a case where no crystalline peak is observed.

From the results shown in Table 1, it can be seen that crystalline tungsten oxide can be effectively formed even at a low temperature by the method according to the present application. Especially, at a deposition temperature in the range of about 250 ° C to 350 ° C, (Examples 1, 3, and 4), or when deposition and heat treatment are performed to satisfy Formula 2 at a deposition temperature in the range of about 250 ° C to 350 ° C (Example 2), a more crystalline tungsten oxide Can be produced.

10: evaporation source (organic tungsten compound)
20: substrate
30: Crucible
40: heat source

Claims (13)

A deposition step of depositing tungsten oxide or the organic tungsten compound on a substrate by holding an organic tungsten compound having a melting point of 300 占 폚 or less at a temperature within a range of 100 占 폚 to 400 占 폚 for a deposition time in a range of 10 minutes to 180 minutes; And a heat treatment step of heat-treating the deposited deposition material, wherein the deposition step is performed so as to satisfy the following equation (1), or the deposition and heat treatment step is performed so as to satisfy the following equation (2)
[Equation 1]
T1 / M ≤ 6 ° C / min
[Equation 2]
T2 / M ≥ 24 ℃ / min
T1 is the temperature at which the organic tungsten compound is held in the deposition step, T2 is the heat treatment temperature in the heat treatment step, and M is the time for depositing the tungsten oxide or organic tungsten compound on the substrate in the deposition step. The method for producing tungsten oxide according to claim 1, wherein the organic tungsten compound has a melting point in the range of 100 占 폚 to 290 占 폚. The method for producing tungsten oxide according to claim 1, wherein the organic tungsten compound is W (CO) 6 or W (OC 6 H 5 ) 6 . The method according to claim 1, wherein the holding temperature of the organic tungsten compound is controlled within a range of 250 ° C to 350 ° C. The method of claim 1, wherein the deposition time of the organic tungsten compound is controlled within a range of from 40 minutes to 80 minutes. The method of claim 1, wherein the absolute value of the difference between the temperature of the substrate and the temperature at which the organic tungsten compound is held during the deposition process is controlled within the range of 175 ° C to 275 ° C. The method of claim 1, wherein the organic tungsten compound is deposited on the substrate to a thickness within a range of 30 to 2000 nm. 2. The method of claim 1, wherein the heat treatment step comprises heating the deposition material to a temperature in the range of 600 占 폚 to 900 占 폚. 9. The method of claim 8, wherein the heating in the heat treatment step is performed for 1 to 5 minutes. The method according to claim 1, wherein the heat treatment is performed in an oxygen atmosphere. The method according to claim 1, wherein the heat treatment step is performed while injecting oxygen gas at a flow rate of 1 to 10 sccm. The method for producing tungsten oxide according to claim 1, wherein the tungsten oxide is crystalline. The method for producing tungsten oxide according to claim 1, wherein the tungsten oxide comprises a tri- or monoclinic crystal structure.
KR1020150056046A 2015-04-21 2015-04-21 Method for preparing tungsten oxide KR101913757B1 (en)

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KR20190129762A (en) * 2018-05-11 2019-11-20 엘지전자 주식회사 Method for preparing transition metal oxide fine particles
WO2019216719A1 (en) * 2018-05-11 2019-11-14 엘지전자 주식회사 Method for manufacture of transition metal oxide fine particles
WO2020084852A1 (en) * 2018-10-25 2020-04-30 Ｊｘ金属株式会社 Molybdenum oxychloride or tungsten oxychloride and method for producing same

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WO2001042534A2 (en) 1999-12-09 2001-06-14 Moltech Invent S.A. Metal-based anodes for aluminium electrowinning cells

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001042534A2 (en) 1999-12-09 2001-06-14 Moltech Invent S.A. Metal-based anodes for aluminium electrowinning cells

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CHEM. VAP. DEPOSITION 2012 18 245-248*

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