JP2006152391A - METAL DOPED TiO2 FILM AND ITS DEPOSITION METHOD - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a deposition method of a metal doped TiO2 film capable of easily changing the content of the doped metal, and the metal doped TiO2 film precisely controlled in the doping amount of the metal. <P>SOLUTION: Pulse packet-like voltages are alternately applied to a first target 21a composed of metal Ti and a second target 21b composed of doped Ti. The light emission wavelength and light emission intensity of the discharge of the Ti at the time of sputtering of the target 21a are detected by a PEM 31a. Also, the light emission wavelength and light emission intensity of the discharge of the Ti at the time of sputtering of the target 21b are made into electric signals via a collimator 30b, a filter and an optical double amplifier and are detected by a PEM (plasma emission monitor) 31b. The sputtering rates of the targets 21a, 21b are calculated and the pulse electric power, pulse amount and pulse width applied to the respective targets 21a, 21b and the amount of oxygen flowing into a cover 26 and the pressure in the cover are controlled based on the results of the calculation. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to a metal-doped TiO ₂ film and a film forming method thereof.

Conventionally, TiO ₂ is an n-type oxide semiconductor, and its thin film and particles are used as an optical film utilizing a photocatalyst and a high refractive index. In recent years, a dye-sensitized solar cell using titanium dioxide has attracted attention as an inexpensive and clean solar cell (for example, JP-A-2003-123853).

However, since TiO ₂ has a low carrier concentration, it has poor conductivity, and control of the amount of carriers has been essential for use in electronic device applications. Therefore, recently, conductivity has been imparted by doping TiO ₂ with Nb.

Conventionally, when a metal-doped TiO ₂ film is formed by sputtering, a reactive sputtering method in which a reactive gas (oxygen) is sputtered using a metal-doped Ti target, or a metal-doped TiO ₂ target is used. An RF sputtering method is used in which sputtering is performed using an RF power source.
JP 2003-123853 A

  According to the reactive sputtering method or the RF sputtering method described above, since the content of the doped metal in the formed film depends on the composition of the target, the doping amount differs every time a film having a different doping amount is formed. It was necessary to prepare a target.

  Further, in the sputtering method, the ratio of Ti and the doped metal in the actually formed film does not necessarily match the ratio of Ti and the doped metal in the target, so that a film having a desired composition is formed. In order to do this, it was necessary to recreate the target many times. That is, first, a target having a certain composition is formed and deposited, the composition of the deposited film is analyzed, and the composition of the target is compared with the composition of the film. Next, it was necessary to follow the procedure of preparing a target with a finely adjusted composition again, forming a film, and adjusting the composition of the formed film.

The present invention solves the above-described problems, and can easily change the content of the doped metal, and the method for forming a metal-doped TiO ₂ film and the metal with a precisely controlled metal doping amount are doped. An object is to provide a TiO ₂ film.

  Further, the conventional reactive sputtering method and RF sputtering method have a low film formation rate and poor productivity.

An object of the present invention is to provide a method for forming a metal-doped TiO ₂ film at high speed as one aspect thereof.

Method for forming the TiO ₂ film doped with a metal according to claim 1 is a method for forming the TiO ₂ film metal-doped by reactive sputtering, in an atmosphere containing oxygen gas, the first consisting of Ti By sputtering using a target and a second target made of a doped metal, a metal-doped TiO ₂ film is formed.

Method for forming the TiO ₂ film doped with a metal according to claim 2 is a method for forming the TiO ₂ film metal-doped by reactive sputtering, in an atmosphere containing oxygen gas, the first consisting of Ti By sputtering using a target and a second target made of Ti containing a doped metal, a metal-doped TiO ₂ film is formed.

Method for forming the TiO ₂ film doped with metal according to claim 3 is a method for forming the TiO ₂ film metal-doped by reactive sputtering, in an atmosphere containing oxygen gas, containing doped metal Ti By sputtering using a first target made of Ti and a second target made of Ti containing the same doped metal as the first target at a different content from the first target A TiO ₂ film is formed.

The method for forming a metal-doped TiO ₂ film according to claim 4 is characterized in that, in any one of claims 1 to 3, the emission wavelength and emission intensity of discharge of Ti and doped metal during sputtering are monitored. It is what.

The method for forming a metal-doped TiO ₂ film according to claim 5 is the method according to any one of claims 1 to 4, wherein the same number of monitors as the target are provided, and light emission of discharge of Ti and doped metal in each target The wavelength and emission intensity are monitored using a corresponding monitor.

A method for forming a metal-doped TiO ₂ film according to claim 6 is the method according to claim 5, wherein at least one of pulse power, pulse amount, pulse width, and pressure during film formation applied to each target is based on the monitoring. The content of the doped metal in the film to be formed and / or the crystallinity of the film to be formed is controlled by changing the thickness.

According to a seventh aspect of the present invention, there is provided a method for forming a metal-doped TiO ₂ film according to the fifth or sixth aspect, wherein the oxygen supply amount is controlled based on the monitoring.

The method for forming a metal-doped TiO ₂ film according to claim 8 is characterized in that in any one of claims 1 to 7, sputtering is performed by applying an intermittent voltage alternately or simultaneously to each target. It is a feature.

A method for forming a metal-doped TiO ₂ film according to claim 9 is the method according to any one of claims 1 to 8, wherein a pulse packet composed of a plurality of pulse voltages is applied alternately or simultaneously to each target. It is characterized by doing.

The method for forming a metal-doped TiO ₂ film according to claim 10 is the method according to any one of claims 1 to 9, wherein charging of the target is prevented by intermittently applying a positive voltage to each target. It is characterized by doing.

The method for forming a metal-doped TiO ₂ film according to claim 11 is the crystal structure and crystal system of the metal-doped TiO ₂ film according to any one of claims 1 to 10, wherein the substrate is heated during sputtering. It is characterized by controlling.

The method for forming a metal-doped TiO ₂ film according to claim 12 is the method according to any one of claims 1 to 11, wherein the doped metal is V, Nb, Ta, Zr, Hf, Sc, Y, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Ag, Au, Zn, Cd, B, Al, Ga, In, C, Si, Ge, It is at least one selected from the group consisting of Sn, Pb, Bi, Sb, Be, Mg, Ca, Sr, Ba, Ra, Li, Na, K, Rb, Cs, Fr, and a lanthanoid element. Is.

Single method for forming the TiO ₂ film doped with metal according to claim 13 is a method for forming the TiO ₂ film metal-doped by reactive sputtering, in which in an atmosphere containing oxygen gas, a metal-doped A sputtering target is applied by intermittently applying a voltage to the target, and the oxygen supply amount is controlled by monitoring the emission wavelength and emission intensity of the discharge of the doped metal and Ti. It is.

The TiO ₂ film doped with metal according to claim 14 is formed by the film forming method according to claims 1 to 13.

In the method of forming a metal-doped TiO ₂ film according to claim 1, sputtering is performed using a first target made of Ti and a second target made of a doped metal. By changing the ratio between the sputtering rate of the second target and the sputtering rate of the second target, a TiO ₂ film doped with a metal having a desired content can be formed only from the two types of targets. .

In the method for forming a metal-doped TiO ₂ film according to claim 2, sputtering is performed using a first target made of Ti and a second target made of Ti containing a doped metal. By forming the film by changing the ratio of the sputtering speed of the first target and the sputtering speed of the second target, a TiO ₂ film doped with a metal with a desired content is formed only from the above two types of targets. can do.

In the method for forming a metal-doped TiO ₂ film according to claim 3, the first target made of Ti containing the doped metal and the first target made of the same doped metal as the first target are: Since sputtering is performed using a second target made of Ti containing at different contents, by changing the ratio between the sputtering rate of the first target and the sputtering rate of the second target, the film is formed. A TiO ₂ film doped with a metal having a desired content can be formed from only the above two types of targets.

In particular, in the method for forming a metal-doped TiO ₂ film according to claims 2 and 3, the first target and the first target are formed even when the content of the doped metal in the film to be formed is small. The difference in sputtering amount between the two targets can be reduced, and a TiO ₂ film doped with metal can be formed more stably and at high speed.

In the method for forming a metal-doped TiO ₂ film according to claim 4, the amount of sputtering of Ti and doped metal is constantly monitored by monitoring the emission wavelength and emission intensity of discharge of Ti and doped metal during sputtering. Can be recognized accurately. Therefore, by controlling the film formation conditions based on the result of this monitoring, it is possible to accurately and stably form a TiO ₂ film doped with a metal with a desired content and controlled in oxidation number. .

In the method for forming a metal-doped TiO ₂ film according to claim 5, the same number of monitors as the targets are provided, and a monitor corresponding to the emission wavelength and emission intensity of discharge of Ti and doped metal in each target is used. Therefore, the discharge status of each target can be recognized individually.

7. The method of forming a metal-doped TiO ₂ film according to claim 6, wherein at least one of pulse power, pulse amount, pulse width, and pressure during film formation applied to each target is changed based on monitoring. By doing so, the content of the doped metal in the film to be formed and / or the crystallinity of the film to be formed can be precisely controlled.

In the method for forming a metal-doped TiO ₂ film according to claim 7, the oxygen supply amount can be precisely controlled by controlling the oxygen supply amount based on monitoring. For this reason, it becomes possible to stably supply a TiO ₂ film doped with a metal whose oxidation number is precisely controlled.

  Moreover, when the supply amount of oxygen becomes excessive, the surface of the target is completely oxidized, and the film formation rate becomes very slow. On the other hand, if the amount of oxygen introduced is too small, the target surface is not oxidized and film formation is performed. However, as described above, since the oxygen supply amount is controlled based on the monitoring, an appropriate amount of oxygen can be introduced based on the density of Ti and the doped metal in the plasma. Thereby, it is possible to perform sputtering in the “transition region” that is an intermediate region between the two supply amount regions. As a result, a film containing an appropriate amount of oxygen can be formed at high speed.

In the method for forming a metal-doped TiO ₂ film according to claim 8, since an intermittent voltage is alternately applied to each target, a large current is allowed to flow through the target to perform stable high-speed film formation. it can. By using this method, abnormal discharge can be significantly suppressed, so that stable long-time discharge is possible and a high-quality film with little damage can be produced.

In the metal-doped TiO ₂ film forming method according to claim 9, since a pulse packet is applied to each target, a larger current flows than when a single pulse is applied to each target. And stable high-speed film formation becomes possible.

The method for forming a metal-doped TiO ₂ film according to claim 10 can cause a large current to flow through each target by intermittently applying a positive voltage to the target to prevent target charging. Stable high-speed film formation is possible.

By heating the substrate during sputtering as in the eleventh aspect, the crystallinity of the metal-doped TiO ₂ film can be controlled.

  As claimed in claim 12, the doped metals include V, Nb, Ta, Zr, Hf, Sc, Y, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni. , Pd, Pt, Ag, Au, Zn, Cd, B, Al, Ga, In, C, Si, Ge, Sn, Pb, Bi, Sb, Be, Mg, Ca, Sr, Ba, Ra, Li, Na , K, Rb, Cs, Fr and at least one selected from the group consisting of lanthanoid elements can be used.

According to the method of the thirteenth aspect, the metal-doped TiO ₂ film can be formed at high speed and with precision.

In the TiO ₂ film doped with metal according to claim 14, the content of the doped metal in the TiO ₂ film is precisely controlled.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

FIG. 1 is a schematic diagram for explaining a method of forming a metal-doped TiO ₂ film according to an embodiment by a dual cathode magnetron sputtering method, and FIG. 2 is an example of a voltage applied to the target electrode of FIG. It is a figure explaining.

  As shown in FIG. 1, a first sputtering unit is composed of a target electrode 20A provided with a first target 21a on a support 20a and a magnet 22a disposed below the target electrode 20A. In addition, a second sputtering unit is configured by a target electrode 20B provided with a second target 21b on the support 20b and a magnet 22b disposed below the target electrode 20B. The first sputtering unit and the second sputtering unit are installed adjacent to each other, and an AC power supply 25 is connected to these sputtering units via a switching unit 24. In the present embodiment, the first target 21a is made of metal Ti, and the second target 21b is made of Ti doped with metal.

  Examples of the doped metal of the second target 21b include V, Nb, Ta, Zr, Hf, Sc, Y, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, and Ir. , Ni, Pd, Pt, Ag, Au, Zn, Cd, B, Al, Ga, In, C, Si, Ge, Sn, Pb, Bi, Sb, Be, Mg, Ca, Sr, Ba, Ra, Li , Na, K, Rb, Cs, Fr and at least one selected from the group consisting of lanthanoid elements are used.

The doping amount (wt%) of the doped metal in the second target 21b is not particularly limited as long as it is equal to or more than the doping amount (wt%) of the doped metal in the TiO ₂ film doped with the metal to be deposited. However, in order to prevent an extreme deviation in the sputtering amount of each target 21a, 21b, the doping amount (wt%) of the doped metal in the second target 21b is doped with the metal to be deposited. It is preferable that it is 1.1 to 10 times, especially 1.2 to 5 times the doping amount (wt%) of the doped metal in the TiO ₂ film.

  These target electrodes 20A and 20B are covered with a cover 26. The cover 26 is connected to a pump (not shown) via an exhaust port 28 and is connected to a gas supply source (not shown) via a gas introduction port 27.

  Collimators 30a and 30b are provided in the cover 26. These collimators 30a and 30b are connected to plasma emission monitors (hereinafter also referred to as PEMs) 31a and 31b through a filter and a light amplification amplifier (not shown). It is connected.

  The PEM is an apparatus that monitors an electrical signal obtained by condensing plasma emission with a collimator and photoelectrically converting it with a photomultiplier tube (PM). The PEM is set to a certain sensitivity and monitors the emission intensity of the plasma.

  As the filter for the target 21a, a filter capable of passing at least the wavelength of 500 to 600 nm of the emission spectrum of Ti is used. As the filter for the target 21b, a filter capable of passing the wavelength of the emission spectrum of Ti and the wavelength of the emission spectrum of the doped metal is used. For the target 21b, two sets of the collimator 30b, the filter, the photomultiplier tube, and the PEM 31b may be used, and each set may be used for Ti detection and dope metal detection, respectively.

When forming a metal-doped TiO ₂ film using the above apparatus, first, the substrate 1 is placed above the targets 21a and 21b in the cover 26, the inside of the cover 26 is evacuated by a pump, A mixed gas containing oxygen in an inert gas or the like is introduced into the cover 26, and the inside of the cover 26 is brought to a predetermined pressure. The oxygen flow rate of this mixed gas is, for example, 1% to 30% with respect to argon.

  As the substrate 1, for example, glass such as alkali silicate glass, non-alkali glass, and quartz glass can be used. Various plastic substrates such as acrylic can also be used. A polymer film substrate such as PET can also be used. The thickness of the substrate is generally 0.1 to 10 mm, preferably 0.3 to 5 mm. The glass plate is preferably chemically or thermally strengthened.

  Next, for example, as shown in FIG. 2, a pulse packet voltage is alternately applied to the target electrodes 20A and 20B to form a glow discharge. As a result, particles are sputtered from the targets 21a and 21b, and these particles adhere to the substrate 1 above the targets 21a and 21b. At this time, the targets 21a and 21b or the sputtered particles are oxidized by oxygen gas.

  The emission wavelength and emission intensity of the Ti discharge during sputtering of the target 21a become an electrical signal through the collimator 30a, the filter, and the optical amplification tube, and are detected by the PEM 31a. Further, the emission wavelength and emission intensity of the discharge of Ti and the doped metal at the time of sputtering of the target 21b become an electrical signal through the collimator 30b, the filter, and the optical doubler, and are detected by the PEM 31b. From these electric signals, the sputtering speed of the first target 21a and the sputtering speed of the second target 21b are calculated, and based on the calculation result, the pulse power, the pulse amount and the pulse width applied to each target 21a, 21b, The amount of oxygen introduced into the cover 26 and the pressure in the cover are controlled.

The pulse power, the pulse amount, and the pulse width vary depending on the volume of the target, the volume in the cover 26, the required film formation speed, and the like. For example, the pulse power is 1 kW to 20 kW, the pulse amount is 5% to 50%, the pulse The width is controlled within a range of 0.1 to 500 msec. When the pulse power is 50 kW or more, abnormal discharge occurs, and a TiO ₂ film doped with a metal whose composition is precisely controlled cannot be stably formed. On the other hand, when the pulse power is 500 W or less. The film formation rate becomes slow. When the pulse amount is 90% or more, continuous discharge occurs, and when the pulse amount is 1% or less, the film formation rate is slow.

  The oxygen supply amount is, for example, about 1 to 50 sccm. If the amount of oxygen introduced is excessive, the surfaces of the targets 21a and 21b are completely oxidized, and the film formation rate becomes very slow. Such a region where the amount of introduced oxygen is excessive is referred to as a “reactive sputtering region”. On the other hand, if the amount of oxygen introduced is too small, the target surface is not oxidized and film formation is performed. Such a region is referred to as a “metallic sputter region”. In the present embodiment, an appropriate amount of oxygen is introduced based on the density of the metal in the plasma by the control described above.

  The pressure in the cover 26 during the film formation is preferably controlled within a range of 0.01 Pa to 30 Pa, particularly 0.1 to 10 Pa.

After the metal-doped TiO ₂ film formed on the substrate 1 has reached a predetermined thickness, the sputtering is finished, and the substrate 1 is laminated with the metal-doped TiO ₂ film in the cover 20 at atmospheric pressure. Take out.

The content of the doped metal in the metal-doped TiO ₂ film is, for example, about 0.1 atm% to 20 atm% with respect to Ti. Further, as the thickness of the TiO ₂ film doped with metal, for example of about 5Å~5μm it can be deposited.

In the method for forming a metal-doped TiO ₂ film according to the present embodiment, sputtering is performed using a first target 21a made of Ti and a second target 21b made of Ti containing a doped metal. Therefore, by changing the ratio of the sputtering rate of the first target 21a and the sputtering rate of the second target 21b, a film having a desired content can be obtained from only the two types of targets 21a and 21b. A TiO ₂ film doped with can be formed.

In the method for forming a metal-doped TiO ₂ film according to the present embodiment, the amount of sputtering of Ti and doped metal is monitored by monitoring the emission wavelength and emission intensity of the discharge of Ti and doped metal during sputtering. Can always be accurately recognized. Therefore, by controlling the film formation conditions based on the result of this monitoring, a TiO ₂ film doped with a metal with a desired content can be formed accurately.

In addition, when a metal-doped TiO ₂ film is produced by controlling the amount of gas introduced using a conventional flow meter, it is difficult to stably control the oxidation number of the metal-doped TiO ₂ film. This is because, for example, the deposition rate changes as the target wears out, and the sputtering conditions including the oxygen flow rate during deposition change. In this embodiment, plasma emission monitor control (PEM) that monitors the emission wavelength and emission amount of Ti and doped metal during film formation and controls the amount of oxygen introduced into the chamber from the density of Ti and doped metal in the plasma. Therefore, it is possible to stably form a TiO ₂ film doped with a metal whose oxidation number is controlled.

  In particular, since the same number of monitors as the targets 21a and 21b are provided and the emission wavelength and emission intensity of the discharge of Ti and doped metal at each target are monitored using the corresponding monitors, the discharge status of each target is individually recognized. be able to.

In the method for forming a metal-doped TiO ₂ film according to the present embodiment, based on monitoring, at least one of pulse power, pulse amount, pulse width, and pressure during film formation applied to each target By changing the above, it is possible to precisely control the content of the doped metal in the film to be formed and / or the crystallinity of the film to be formed.

Moreover, the oxygen supply amount can be precisely controlled by controlling the oxygen supply amount based on monitoring. For this reason, it becomes possible to stably supply a TiO ₂ film doped with a metal whose oxidation number is precisely controlled. Further, by introducing an appropriate amount of oxygen, sputtering in the “transition region” becomes possible, and as a result, a film containing an appropriate amount of oxygen can be formed at a high speed.

In the method for forming a metal-doped TiO ₂ film according to the present embodiment, an intermittent voltage is alternately applied to the targets 21a and 21b, so that a large current is passed through the targets and stable high-speed formation is achieved. A membrane can be performed. By using this method, abnormal discharge can be significantly suppressed, so that stable long-time discharge is possible and a high-quality film with little damage can be produced.

  In addition, a single pulse may be applied to each target 21a, 21b, but as shown in FIG. 2, a single pulse is applied to each target 21a, 21b by applying a pulse packet to each target 21a, 21b. A larger current can be flowed than when the voltage is applied, and stable high-speed film formation is possible.

  The above embodiment is an example of the present invention, and the present invention is not limited to the above embodiment. For example, in the above embodiment, a Ti target is used as the first target 21a. However, when a film having a high content of the doped metal is formed, the first target 21a is the same as the second target. You may use the target which consists of Ti which contains dope metal by the content rate different from a 2nd target. Moreover, when there is more dope metal content in the film | membrane to form into a film, you may use the 1st target which consists of Ti, and the 2nd target which consists of dope metal.

  Further, although a negative voltage is normally applied to the target, the target may be prevented from being charged by intermittently applying a positive voltage to the target. In this case, since the charge accumulated in the target due to the negative voltage is eliminated by the positive voltage, formation of an insulating film such as an oxide on the edge of the target during sputtering can be suppressed. Thereby, a large current can be passed through each target, and stable high-speed film formation is possible.

Further, the crystallinity of the metal-doped TiO ₂ film may be controlled by heating the substrate during sputtering.

  In the above embodiment, the number of the first target electrodes 20A and the number of the second target electrodes 20B is one, but two or more each may be used.

  In the above embodiment, the bipolar dual magnetron sputtering method in which the common switching unit 24 is installed in the two sputtering units is used. However, the unipolar dual magnetron sputtering method in which the switching unit is individually installed in each sputtering unit is used. Also good.

  Hereinafter, Example 1 and Comparative Example 1 will be described, but the present invention is not limited to Example 1.

<Example 1>
Film formation was performed using the apparatus of FIG. As the first target, a Ti target doped with Nb at 10 atm% (vertical 999 mm × horizontal 150 mm × thickness 5 mm) was used. As the second target, a Ti target not doped with metal (vertical 999 mm × width 150 mm × thickness 5 mm) was used. A non-alkali glass 7059 (length 80 mm × width 25 mm × thickness 1.1 mm) manufactured by CORNING was used for the substrate.

First, the substrate was introduced into the cover, the inside of the cover was evacuated to 9 × 10 ⁻⁴ Pa or less by a pump, and then a mixed gas containing oxygen in argon was introduced into the cover 26. Then, to prepare a Nb-doped TiO ₂ film by applying a pulse voltage alternately to the target electrode.

  The pulse frequency was 50 Hz. Regarding the amount of introduced oxygen, a necessary and sufficient amount of oxygen not causing oxygen deficiency was introduced by monitoring the amount of plasma emission of Ti. The amount of oxygen introduced was about 5 to 20 sccm. The pressure during film formation was also controlled by monitoring the amount of Ti plasma emission. The pressure during film formation was about 0.3 to 10 Pa.

Here, the duty ratio (pulse width ratio) between the target 1 and the target 2 was changed in increments of 20 from 100: 0 to 0: 100, and films were formed under the respective conditions. The applied power when the duty was 100 was 5 kW. The pulse amount was 50%. As a result, Nb-doped TiO _{2 in} which the doping amount of Nb was continuously changed from 0 to 10 atm% could be produced. When the amount of doping was analyzed by ESCA, they were 0, 2.8, 4.5, 6.3, 8.2, and 10 atm% almost in proportion to the duty ratio. The film formation rate was 10 mm · m / min when the duty ratio was 100: 0 (no metal doping), and 19.2 mm · m / min when the duty ratio was 0: 100.

<Comparative example 1>
Using a Ti target doped with 5 atm% of Nb, an Nb-doped TiO ₂ film was produced by a normal reactive sputtering method. When the obtained film was measured with a level difference measuring device and the film formation rate was determined, it was 0.4 mm · m / min, and the rate was very slow.

It is the schematic for demonstrating the dual cathode system magnetron sputtering method. It is a figure explaining an example of the voltage applied to the target electrode of FIG.

Explanation of symbols

1 Substrate 20a, 20b Support 20A, 20B Target electrode 21a, 21b Target 22a, 22b Magnet 24 Switching unit 25 AC power supply 26 Cover 27 Gas inlet 28 Exhaust outlet 30a, 30b Collimator 31a, 31b PEM

Claims (14)

In the method of forming a metal-doped TiO ₂ film by reactive sputtering,
A metal-doped TiO ₂ film is formed by sputtering using a first target made of Ti and a second target made of a doped metal in an atmosphere containing oxygen gas. A method for forming a metal-doped TiO ₂ film. In the method of forming a metal-doped TiO ₂ film by reactive sputtering,
Forming a metal-doped TiO ₂ film by sputtering using a first target made of Ti and a second target made of Ti containing a doped metal in an atmosphere containing oxygen gas A method for forming a metal-doped TiO ₂ film characterized by the following. In the method of forming a metal-doped TiO ₂ film by reactive sputtering,
A first target made of Ti containing a doped metal in an atmosphere containing oxygen gas, and a second target made of Ti containing the same doped metal as the first target at a different content from the first target A metal-doped TiO ₂ film is formed by sputtering using a target with a metal, and a metal-doped TiO ₂ film is formed. 4. The method for forming a metal-doped TiO ₂ film according to claim 1, wherein the emission wavelength and emission intensity of discharge of Ti and doped metal during sputtering are monitored. 5. The monitor according to claim 1, wherein the same number of monitors as the target are provided, and the emission wavelength and emission intensity of discharge of Ti and doped metal in each target are monitored using a corresponding monitor. A method for forming a metal-doped TiO ₂ film. 6. The doped metal in the film to be formed according to claim 5, by changing at least one of pulse power, pulse amount, pulse width, and pressure during film formation applied to each target based on the monitoring. A method for forming a metal-doped TiO ₂ film, wherein the content and / or crystallinity of the film to be formed is controlled. 7. The method for forming a metal-doped TiO ₂ film according to claim 5, wherein an oxygen supply amount is controlled based on the monitoring. In any one of claims 1 to 7, each target alternately or simultaneously, TiO ₂ film forming method that metal-doped and performing sputtering by applying intermittent voltage. In any one of claims 1 to 8, alternately or simultaneously a pulse packet comprising a plurality of pulse voltages each target, TiO ₂ film method deposition doped with metal, characterized in that the intermittently applied . 10. The method for forming a metal-doped TiO ₂ film according to claim 1, wherein charging of the target is prevented by intermittently applying a positive voltage to each target. . 11. The formation of a metal-doped TiO ₂ film according to claim 1, wherein the crystallinity and crystal system of the metal-doped TiO ₂ film are controlled by heating the substrate during sputtering. Membrane method. 12. The doped metal according to claim 1, wherein the doped metal is V, Nb, Ta, Zr, Hf, Sc, Y, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co. , Rh, Ir, Ni, Pd, Pt, Ag, Au, Zn, Cd, B, Al, Ga, In, C, Si, Ge, Sn, Pb, Bi, Sb, Be, Mg, Ca, Sr, Ba , Ra, Li, Na, K, Rb, Cs, Fr and at least one selected from the group consisting of lanthanoid elements, a method for forming a metal-doped TiO ₂ film. In the method of forming a metal-doped TiO ₂ film by reactive sputtering,
Using a single Ti target doped with metal in an atmosphere containing oxygen gas, sputtering is performed by intermittently applying a voltage to the target, and the emission wavelength and emission intensity of the discharge of the doped metal and Ti are monitored. And a method for forming a metal-doped TiO ₂ film, wherein the oxygen supply amount is controlled. A metal-doped TiO ₂ film formed by the film forming method according to claim 1.

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