JPH03187733A - Amorphous oxide film, preparation thereof and target thereof - Google Patents

Abstract

PURPOSE:To obtain a protective film with good stability and excellent wearing resistance by using an oxide contg. at least one selected from Zr, Ti, Hf, Sn, Ta and In and at least one from B and Si as a main ingredient. CONSTITUTION:An oxide contg. at least one selected from Zr, Ti, Hf, Sn, Ta and In and at least one selected from B and Si is a main ingredient for an amorphous oxide film. This amorphous oxide film is a thin film with excellent scuff resistance, wearing resistance and chem. durability as well as freedom for optical designing. To make the film amorphous and to improve thereby scuff resistance and reliability, it is pref. that the total of oxides selected from B2O3 and SiO2 is especially 20 pts. or more to 100 pts. total of oxides selected from TiO2, ZrO2, HfO2, SnO2, Ta2O3 and In2O3 at a molar ratio. In addition, when B2O3 is used, if the amt. of B2O3 is too much, as reliability, especially chem. durability is lowered, it is pref. that it is 50 pts. or less at a molar ratio based on 100 pts. total of the selected oxides depending on the use. When SiO2 is used, if the amt. of SiO2 is too large, as durability to alkali decreases, it is pref. that the amt. is especially 400 pts. or less at a molar ratio based on 100 pts. total of the selected oxides.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an amorphous oxide film that is transparent and has excellent durability, and a method for producing the same.

[Conventional technology J] Conventionally, optical functions have been added by forming a thin film on a transparent substrate such as glass or plastic, such as mirrors, heat-reflecting glass, low-emission glass, interference filters, and anti-reflection for camera lenses and eyeglass lenses. There are coats etc.

In a normal mirror, Ag is formed by an electroless plating method, or AI, Cr, etc. are formed by a vacuum evaporation method, a sputtering method, or the like. Among these, the Cr film is relatively strong, so it is partially used as a surface mirror with an exposed coated surface.

Heat-reflective glass has been formed using titanium oxide, tin oxide, or the like by a spray method, a CVD method, or a dipping method. Recently, metal films, nitride films, tin-doped indium oxide (ITOL, etc.) formed on the glass plate surface by sputtering have come to be used as heat-reflecting glasses.The sputtering method allows for control of film thickness. It is easy to form multiple films in succession, and when combined with a transparent oxide film, it is possible to design transmittance, reflectance, color tone, etc.Therefore, it is in demand for architectural applications where design is important. It's growing.

Low-emission glass (Low-EmisSivity glass) reflects indoor heating and radiant heat from walls towards the indoor side.
It has a structure such as a three-layer system of ZnO/Ag/ZnO in which silver is sandwiched between zinc oxides or a five-layer system of ZnO/Ag/ZnO/Ag/ZnO (see Japanese Patent Application No. 61-280644). Used in the form of laminated glass. In recent years, its popularity in cold regions of Europe has been remarkable.

Anti-reflection coatings for lenses, etc., are made by alternately laminating high refractive index films such as titanium oxide or zirconium oxide and low refractive index films such as silicon oxide or magnesium fluoride. Usually, a vacuum evaporation method is used. When forming a film, the substrate is heated to improve scratch resistance.

[Problems to be Solved by the Invention] Antireflection coatings for surface mirrors, single-panel heat-reflecting glasses, lenses, and the like are used with the coated film exposed to the air. Therefore, it must have excellent chemical stability and wear resistance. On the other hand, even low-emissivity glass can be defective due to scratches during transportation or handling before it is made into double-glazed or laminated glass. For this reason, there is a need for a protective film that is stable and has excellent abrasion resistance, or for an optical thin film that also serves as a protective film.

To improve durability, a chemically stable and transparent oxide film is usually provided on the air side. These oxide films include titanium oxide, tin oxide, tantalum oxide, zirconium oxide,
Silicon oxide and other materials have been selected and used depending on the required performance.

However, although titanium oxide and zirconium oxide have excellent chemical stability, they tend to form crystalline films with large irregularities on the surface, which increases friction when rubbed and has poor wear resistance. .

On the other hand, tin oxide and silicon oxide are weak against acids and alkalis, respectively (
It cannot withstand long-term immersion. Among these, tantalum oxide has both wear resistance and chemical stability, but its wear resistance is still not sufficient.

In addition, titanium oxide, tin oxide, tantalum oxide, and zirconium oxide have relatively high refractive indexes (on the other hand, silicon oxide has a relatively low refractive index, which limits the degree of freedom in optical design when providing various optical functions. There is.

As described above, there is no known thin film that has both high durability and a wide degree of freedom in optical design.

[Means for Solving the Problems] The present invention has been made to solve the above-mentioned problems. At least one of Zr, Ti, Hf, Sn, Ta, and In, B (boron), and Si ) an amorphous oxide film whose main component is an oxide containing at least one kind of
Then, a substance containing at least one of Zr, Ti, Hf, Sn, Ta, and In and at least one of B and Si is sputtered to produce Zr and Ti.

It is characterized by producing an amorphous oxide film whose main component is an oxide containing at least one of Hf, Sn, Ta, and In and at least one of B (boron) and Si (silicon). Zr, Ti, Hf, Sn,
A method for producing an amorphous oxide film whose main component is an oxide containing at least one of Ta and In and at least one of B and Si, and Zr, Ti, Hf, Sn
, Ta, and In; and at least one of B and Si.

The present invention provides that an amorphous oxide containing at least one of Zr, Ti, Hf, Sn, Ta, and In and at least one of B and Si has scratch resistance, abrasion resistance, and chemical durability. This was achieved by discovering that it is a thin film with excellent optical properties and flexibility in optical design.

The composition of the amorphous oxide film of the present invention is not particularly limited, but in order to make the film amorphous and improve scratch resistance and reliability, titanium, zirconium, hafnium, tin, tantalum, indium, boron, etc. , silicon oxide films are TiOx and Zr0, respectively.
g, Hf0z, Snow.

When expressed as TatOs, IngOs, BzOs, 510g, TiOz.

Zr0t, Hf0z, Snow, Ta1ls and In
For a total of 100 parts of oxides selected from 1 Oa, B
The total amount of oxides selected from ias, SiO□ is preferably 5 parts or more, preferably 10 parts or more, particularly 20 parts or more in molar ratio. In addition, in the case of B and O, if there are too many, reliability, especially chemical durability, decreases, so depending on the application,
Ti0g, Zr0g, Hf0t, Sn0m, Tat
200 parts or less in molar ratio, preferably 100 parts or less, based on a total of 100 parts of oxides selected from Os and InJs,
Particularly good is 50 copies or less. In the case of 5ins, TiOx is used because if it is too large, the durability against alkali will decrease.

Zr0t, HfO2, Snow, TatOs and Ing
1900 parts or less, preferably 900 parts or less, particularly 40 parts by molar ratio based on a total of 100 parts of oxides selected from Os.
0 copies or less is better.

Table 1 shows the properties of various amorphous oxide films of the present invention. Films were formed by reactive sputtering using targets with the compositions listed in the table.

Even if the same target is used, there may be slight variations depending on the film composition and film forming conditions, so Table 1 shows only one example.

Crystallinity was observed by thin film X-ray diffraction.

In addition, the scratch resistance is the result of a scratch test using a sand eraser.
○ indicates that there were almost no scratches, and × indicates that scratches were easily generated.

As for wear resistance, as a result of a taper test (wearing wheel C5-10F, load 500 g, 1000 rotations), a haze of less than 4% was rated 01, and a haze of more than 4% was rated poor. Acid resistance was determined by immersion in 0.1N H,SO for 240 hours.
TV (visible light transmittance), RV (visible light reflectance) changes within 1% from before immersion are 0, 1 to 4% are △, and the film has dissolved and disappeared. was marked as ×. Alkali resistance was immersed in O, IN NaOH for 240 hours, resulting in a 1% change in Tv and Rv compared to before immersion.
Those within 2% were rated as ○, those within 2% were rated as Δ, and those in which the film had dissolved were rated as ×. The boiling test is 1 atm, 10
After being immersed in water at 0° C. for 2 hours, the rate of change in TV and Rv from before immersion was rated ◯ if it was within 1%, and the rate of change was rated × if it was over 1%.

Regarding the ZrBxOy film, as is clear from Table 1,
It can be seen that when the amount of B in the film is small, a crystalline film tends to be formed, and when the amount of B is large, an amorphous film tends to be formed. It can also be seen that the crystalline film has poor scratch resistance and abrasion resistance, whereas the amorphous film has excellent scratch resistance and abrasion resistance. This is an amorphous film.
This is thought to be due to the smooth surface. Therefore, Zr
BxOy film (atomic ratio X of B to Zr in the film is 0.1
The film <x) has excellent scratch resistance and abrasion resistance. B20
．． Since the film is hygroscopic and absorbs moisture in the air and dissolves, it is preferable that x<4 for the ZrBxOy film.

There is no particular limit to the atomic ratio of 0 (oxygen) to Zr in the ZrBxOy film, but if it is too high, the film structure will become rough and uneven, and if it is too low, the film will become metallic and the transmittance will decrease. ZrO and B,03
It is preferable that the amount is such that a composite system of ZrO*+XBO+, s is obtained.
When X is included in the atomic ratio to Zr, y=2+1.
It is preferable that it is about 5x.

Furthermore, from Table 1, it can be seen that as the amount of B in the ZrBxOy film increases, the refractive index of the film tends to decrease. The relationship between the film composition and the refractive index n is shown in FIG. 1(a). By increasing the amount of B in the film, the refractive index n decreases from about 2.14 to about 1.46.

Therefore, the zrBxoy film with 0.1 < x < 4.2 < y < 8 has good scratch resistance and abrasion resistance, and is suitable for the purpose of the present invention since the refractive index can be freely selected depending on the amount of B. It is an amorphous oxide film.

Furthermore, as shown in Table 1, as the content of B in the film increases, the acid resistance and alkali resistance tend to deteriorate. When X≧2.3, the acid resistance becomes poor (and when X≧4, the alkali resistance decreases and shows deterioration in the boiling test. For applications requiring durability, ZrBxOy(x
<2.3) is preferable, and ZrBx
The film of O, (x≧2.3) can be used as a low refractive index film in other applications.

As described above, by adding B to the ZrO□ film, the film becomes amorphous and the surface becomes smooth, which is thought to contribute to the improvement of wear resistance and scratch resistance. In addition, the refractive index can be adjusted by the amount of B, and since the internal stress is smaller than that of the Zr0m film, it is advantageous in terms of adhesion to the substrate (glass, plastic, etc.) and the underlying film on the substrate. be. This is especially advantageous when forming thick films.

Next, ZrSi, 0. Regarding the film, as shown in Table 1, a film that is amorphous and has high scratch resistance and abrasion resistance can be obtained.

The refractive index varies depending on the composition ratio between ZrO* (n = 2.14) and 5ift (n = 1.46) (see FIG. 1(b)).

In the Zr5ixOy film, 0.05≦z (Zr in the film
It is preferable that the atomic ratio of Si to Si is less than 19.

If z<0.05, the film will not become amorphous and sufficient physical durability will not be obtained, and if 2≧19, the alkali resistance will be poor. The atomic ratio of O (oxygen) to Zr) is, for the same reason as described for the ZrBxOy film, when the atomic ratio of Si to Zr is 2, considering it as a composite system of ZrO and 5ins. Preferably, y=2+2zN degrees.

Therefore, for applications where it is used in an exposed state in the air, 0.
A ZrSx*Oy film with 05≦z<19.2.1≦y<40 is preferable, and a ZrSxm0y film with 19≦Z can be used as a low refractive index film in other applications.

Further, a ZrBxSxxOy film is also a film suitable for the purpose of the present invention. In such a film, the atomic ratio x of B to Zr, the atomic ratio z of Si, and the atomic ratio y of O (oxygen) are x+z≧0.0.
A value of 5 is preferable because the film becomes amorphous and has high scratch resistance and wear resistance.

Moreover, if x+z<19, the alkali resistance is also good, so ZrB, Si, 0. For membranes, 0.05≦X+
Preferably, z<19. However, as mentioned above,
B20. Since it is hygroscopic and dissolves by absorbing moisture in the air, it is better not to contain too much in the zrBxSitOy film. Specifically, in the film, 0 (oxygen)
For the total amount of Zr, B, and Si excluding
atomic %, and Si < 25 atomic %, the balance is B
If it contains, chemical durability will be insufficient. That is,
Z r B x S l * Zr:B:S in Oy film
If i (atomic ratio) is 1:x:z, 1/(1+x
+ z) <0.25, and z/(1+x+z) <0
．． 25, i.e. x+z-3>0 and x-3z+1>O
The composition of y is ZrB+, which has unfavorable chemical durability.
For the same reason as mentioned in the case of aOy, this film is
Considering a composite system of r0=+B*Om+5lots, y is preferably about 2+1.5x+2z, and therefore preferably about 2<y<40. The larger the content of B or Si, the lower the refractive index of the ZrB, Si, O, film.

An example of a ZrB+51m0y film is shown in FIG. 1(c).

Metals other than Zr, i.e. Ti, Hf, Sn, Ta
, In, and at least one of B and Si also becomes amorphous, providing sufficient scratch resistance and abrasion resistance. Ti51m0. The membrane is shown as sample 28 in Table 1 by way of example.

The amorphous oxide film of the present invention includes Zr, Ti, Hf, and Sn.

Elements other than Ta, In, B, Si, and O, such as P and As, which are glass constituent elements like B and Si, can be used to improve durability, adjust optical constants, stability during film formation, or film formation speed. It may be included in a trace amount to improve the ring.

The thickness of the amorphous oxide film of the present invention is usually 100 to 5000.
Preferably a person. If it is too thin, sufficient scratch resistance cannot be obtained, and if it is too thick, the film tends to peel off (and productivity is also poor).

As a method for manufacturing the amorphous oxide film of the present invention, a wet method such as a spray method, a CVD method, a vapor deposition method, a sputtering method, an ion blating method, and other film forming methods can be used.
The manufacturing method is not particularly limited. However, among these methods, the sputtering method does not melt the raw materials (it has good control and reproducibility of the film composition, and the energy of the particles reaching the substrate is high (it produces a film with good adhesion). , the amorphous oxide film of the present invention can be easily obtained.

In the sputtering method, a film is formed in a glow discharge plasma, so no particular voltage is applied to the substrate (it is known that floating potentials of several to tens of volts occur even if the voltage is applied to the substrate. Some of them are accelerated by this floating potential and enter the substrate during film formation.As a result, some of the atoms that make up the film are implanted at the boundary with the substrate or underlying film, forming a mixed layer. The sputtering method strengthens the bond between the eyebrows, and the atoms on the outermost surface of the film are effectively rearranged during film formation, promoting the densification of the film. Compared to film methods such as vapor deposition, it is possible to obtain a film that is denser, has greater film hardness, and has excellent adhesion to the substrate or underlying film.In addition, by making the film structure more dense, pores and lattice Structural defects such as interatomic atoms that cause film stress are reduced, and this combined with the effect of making the film structure amorphous by adding network former components such as Si and B oxides It also has a remarkable effect on reducing film stress. Also, like Zr oxide, Si oxide itself has a much higher hardness than ordinary soda lime glass, so two components containing Si oxide film,
With three-component films, in addition to the effects of making the film structure more amorphous and denser due to the multicomponent structure, high film hardness can also be achieved in terms of materials.As mentioned above, by using the sputtering method, In addition to the effects of multi-component film composition, it also provides denser film, good adhesion, low film stress, and high film hardness. Properties essential for achieving excellent mechanical durability, such as scratch resistance, can be further improved. As a result, the film of the present invention produced by sputtering exhibits excellent scratch resistance.

The ZrSi,O, film can also be formed by a wet method, such as a sol-gel method. However, in manufacturing methods using such metal-organic substances, a firing process at several hundred degrees Celsius (usually 600 to 850 degrees Celsius) is required in order to completely carry out the decomposition reaction of the raw materials, the removal of organic components, and the progress of the sintering reaction. Ru. Therefore, when the processing temperature is limited due to thermal deterioration of other film materials that make up the coating or process costs, wet methods may leave undecomposed raw materials or organic components in the film, or densify the structure due to the calcination reaction. A serious problem arises in that the chemical or mechanical durability of the membrane is significantly reduced. On the other hand, in the sputtering method,
With the mechanism described above, a film with excellent chemical and mechanical durability can be obtained without particularly heating the substrate. Of course, it is also possible to form a film on a heated substrate if necessary.

As mentioned above, the sputtering method is more preferable than other manufacturing methods.
When forming the amorphous oxide film of the present invention by sputtering, Zr, Ti, Hf, and Sn are used.

A non-oxide target or electrode consisting of at least one of Ta and In (referred to as M) and at least one of boron (B) and silicon (Si) can be used. For example, ZrBmO, , Zr5ixty, Zr
When forming a film such as BmSimOy, zirconium boride single system, zirconium silicide single system, zirconium boride-metal zirconium composite system, zirconium boride-zirconium silicide composite system, zirconium boride-metal Silicon composite system, zirconium boride-boron composite system, zirconium silicide-metal zirconium composite system, zirconium silicide-boron composite system, zirconium silicide-metal silicon composite system, zirconium boride-zirconium silicide-metal zirconium composite system , using a target or electrode of a non-oxide single system or a non-oxide composite system such as a zirconium boride-zirconium silicide-metallic silicon composite system or a zirconium boride-zirconium silicide-boron composite system, I x 1 in a mixed atmosphere of
A uniform film can be formed by reactive sputtering in a vacuum of about 0-3 to 10-'' Torr.I
If it is less than 10-” Torr, the discharge becomes unstable and the I
If the temperature exceeds X 10-” Torr, the sputtered particles will collide with each other and the film formation rate will slow down. Since these non-oxide targets are electrically conductive, they can be formed using DC sputtering. A uniform film can be formed over a large area at high speed.

When performing reactive sputtering using a non-oxide target, B, S and Zr in the target
As is clear from Table 1, the ratio of i tends to be almost maintained in the film formed using the target.

Considering the above trends, ZrB, 0. (0,
1<x<4.2<y<8) When a film is formed by reactive sputtering, Zr91 to 20 atomic %, B9 to
It is preferable to use a target or electrode consisting of 80 atom %. Also, Z r S t x OyZrB11S
Similarly, for the izOy film, Table 2 shows the film desired to be formed and the composition of the target or electrode required therefor.

Alternatively, an oxide target containing at least one of Zr, Ti, Hf, Sn, In, and Ta and at least one of boron and silicon may be used, with Ar as the main component, and appropriate oxygen. The film can also be formed by RFB (high frequency) sputtering in a vacuum of about IX1G-"IX10-"Torr in a non-reducing atmosphere mixed with the following. If it is less than 1 x 10-'' Torr, the discharge becomes unstable, and if it is more than I x 10-'' Torr, sputtered particles collide with each other, resulting in a slow film formation rate. For example, when forming an oxide film containing at least one of Zr, B, and Si, the oxide target may include at least one of boron oxide, silicon oxide, and zirconium oxide (stabilized or partially (including stabilized zirconia), such as zirconium oxide-boron oxide composite system, zirconium oxide-
A silicon oxide composite target or a zirconium oxide-boron oxide-silicon oxide composite target can be used. Table 2 shows the preferred target composition range in this case.

When performing reactive sputtering using a non-oxide target, a transparent film can be formed by increasing the proportion of oxygen in the atmospheric gas, but the deposition rate gradually decreases (
Therefore, in order to form a film at a high speed, it is necessary to keep the oxygen concentration in the atmospheric gas to a certain level, that is, to form a film within the oxygen concentration range of the transition region from an absorbent film to a transparent film. Thus, it is very effective to control sputtering in the transition region.On the other hand, sputtering using a complete oxide target produces a transparent film, but the deposition rate is relatively slow. Therefore, by using a target made of a partially oxidized substance, a stable and transparent film can be formed at high speed. For such a purpose, it is made of at least one of zirconium oxide (including stabilized zirconia), boron oxide, and silicon oxide, and at least one of metal zirconium, boron, metal silicon, zirconium boride, and zirconium silicide. Targets of oxide and non-oxide composite systems, such as oxide composite systems, such as zirconium oxide-zirconium boride composite systems, boron oxide-zirconium boride composite systems, and silicon oxide-zirconium boride composite systems, may also be used. can.

The composition of such a target may be an appropriate mixture of the "non-oxide target" and "oxide target" shown in Table 2 so as to adjust the degree of oxidation of the target to the required degree. Therefore, the composition of such a target is "
The range shown in the column ``Mixed target of oxide and non-oxide'' is preferable.When forming a film using such a target, the sputtering atmosphere should be such that the target is not oxidized so that non-oxide components can be oxidized. It should be decided according to the degree.

The amorphous oxide film of the present invention may be formed by using the above-described oxide target or oxide-non-oxide composite target as a tablet for vapor deposition, and heating and evaporating it with an electron beam or the like. . The vapor deposition method is preferable when manufacturing a multilayer film using light interference because it is easier to precisely control the film thickness than a wet method such as a spray method.

The composition of the target and the composition of the film formed using it are:
Since it varies somewhat depending on the film forming conditions, it cannot be determined unambiguously. The example listed in Table 1 is one example.

The aforementioned electrode or target can be formed, for example, by the following method. Zirconium metal, boron, silicon metal, zirconium boride, zirconium silicide,
Zirconium oxide (Yaks, CaOJgO, etc.)
At least one powder or mixed powder of at least one of (including stabilized or partially stabilized zirconia added with 811o1%), boron oxide, and silicon oxide is pressed at high temperature and high pressure.
The single or composite electrode or target of the present invention is formed by high-pressure pressing or by firing the high-pressure press body. In this case, the particle size of the powder is 0.05
μIl to 40 μm is suitable. In addition, a total of 2wt of iron, aluminum, magnesium, calcium, yttrium, manganese, and hydrogen was added to the aforementioned electrode or target.
It was confirmed that the characteristics are the same even if the carbon content is 20 wt% or less (because carbon disappears as 602 during film formation), the electrode of the present invention Alternatively, a similar effect can be obtained by mixing impurities such as copper, niobium, vanadium, chromium, molybdenum, tungsten, cobalt, rhodium, iridium, etc. into the target.

[Action] When B and/or Sl are added to oxides of Zr, Ti, Hf, Ta, In, and Sn, B and/or Si
is believed to destroy the lattice of such oxides, hinder the growth of crystal grains of such oxides, and make the film more amorphous.

It is thought that an amorphous film has fewer irregularities on the film surface than a film that is an aggregation of microcrystals, and as a result, the amorphous film of the present invention is thought to have a reduced coefficient of friction. For this reason, the amorphous film of the present invention has excellent lubricity and is less prone to catching, so it is thought to be less prone to scratches due to friction and to provide high scratch resistance and high wear resistance.

[Effects] According to the present invention, it is possible to provide a thin film that is highly durable and also has a degree of freedom in optical design in which the refractive index can be controlled by the amount of B and/or Si added.

Further, according to the manufacturing method of the present invention, such a highly durable amorphous oxide film can be uniformly formed over a large area at high speed.

Since the amorphous oxide film of the present invention has high scratch resistance and high abrasion resistance, it can be used as an overcoat for various articles. For example, it can be formed directly on a substrate such as glass, plastic, or other substrates or films to prevent scratches on the surface. It is ideal for glass with other functional films, protection plates for the reading section of barcode readers, anti-reflection films, outermost layers of eyeglass lenses, etc.It is also used in a wide range of mechanical elements, and is a coating material for sliding parts. It can also be used for

In particular, ZrB-Oy (0,1<x<2
．． 3,2<y<5.5) film, Zr5ixOy (0
,05≦z<19.2.1≦3r<40) film, ZrB,
Si, O, (0,05≦x+z<19 (where x+z−
3>O, and x-3z+1>O (excluding compositions),
2<y<40) The film has not only scratch resistance and abrasion resistance, but also excellent chemical durability, so it is suitable for applications in harsh environments, such as architectural and veneer applications. It can be used as a protective layer in the outermost layer of heat-reflecting glass for vehicles and the like.

As mentioned above, the amorphous oxide film of the present invention can change the refractive index with a considerable degree of freedom, so even when it is used as the outermost layer of a multilayer coating film to also serve as a protective layer, it can be used as a protective layer. Because interference, etc. can be controlled freely, it can be easily incorporated into a wide range of multilayer films (and has a very wide range of applications).

[Brief explanation of drawings]

FIG. 1(a) is a diagram showing the relationship between the content of B in a ZrBmOy film and the refractive index n of the film. Figure 1(b) shows Zr
Figure 1(e) shows the relationship between the Si content in the 5zaOy film and n.
Figure 1 (d) shows the relationship between the content of Ti and n.
This is a diagram showing the relationship between the Si content and n in the 5ixOy film. Figure (a) Figure (C) 00 Figure (b)

Claims (1)

[Claims] 1. A non-containing material whose main component is an oxide containing at least one of Zr, Ti, Hf, Sn, Ta, and In, and at least one of B (boron) and Si (silicon). Crystalline oxide film. 2. The main component is an oxide (ZrB_xO_y) containing Zr (zirconium) and B (boron), and the atomic ratio x of boron to zirconium in the film is 0.1<x<4, and the atomic ratio of oxygen to zirconium is The amorphous oxide film according to claim 1, wherein the ratio y is 2<y<8. 3. The main component is an oxide (ZrB_xO_y) containing Zr (zirconium) and B (boron), and the atomic ratio x of boron to zirconium in the film is 0.1<x<2.3, and the atomic ratio x of boron to zirconium in the film is 0.1<x<2.3. Atomic ratio y is 2<y<5
．． 5. The amorphous oxide film according to claim 1, wherein: 4. The main component is an oxide (ZrSi_xO_y) containing Zr (zirconium) and Si (silicon), and the Zr of Si
The amorphous oxide film according to claim 1, wherein the atomic ratio z of oxygen to Zr is 0.05≦z<19, and the atomic ratio y of oxygen to Zr is 2.1≦y<40. 5. The main component is an oxide (ZrB_xSi_zO_y) containing Zr (zirconium), B (boron), and Si (silicon), and the atomic ratio of boron to zirconium in the film is x, the atomic ratio of Si to zirconium is z, and the atomic ratio of oxygen is Zr
Claim 1, wherein the atomic ratio y to amorphous oxide film. 6. Sputtering a substance containing at least one of Zr, Ti, Hf, Sn, Ta, and In and at least one of B and Si to produce Zr, Ti, Hf, Sn, and Ta.
, Zr, characterized in that it produces an amorphous oxide film whose main component is an oxide containing at least one of In and at least one of B (boron) and Si (silicon),
A method for producing an amorphous oxide film whose main component is an oxide containing at least one of Ti, Hf, Sn, Ta, and In and at least one of B and Si. 7. Zr and B An amorphous oxide whose main component is an oxide (ZrB_xO_y) containing B, the atomic ratio x of B to Zr is 0.1<x<4, and the atomic ratio y of oxygen to Zr is 2<y<8. An oxide containing Zr and B (ZrB_xO_y, 0.1<x<4, 2<
A method for producing an amorphous oxide film containing y<8) as a main component. 8. Zr (zirconium) 1 to 96 atom%, Si (silicon) 1 to 95 atom%, O (oxygen) 0 to 67 atom%
By sputtering a target whose main component is an oxide containing Zr and Si (ZrSi_zO_y), the atomic ratio z of Si to Zr is 0.05.
≦z<19, and the atomic ratio y of oxygen to Zr is 2.
Oxide containing Zr and Si (ZrSi_zO_y) characterized by producing an amorphous oxide film with 1≦y<40
, 0.05≦z<19, 2.1≦y<40). 9. The content of Zr (zirconium) is a (atomic %), B
If the content of (boron) is b (atomic %), the content of Si (silicon) is c (atomic %), and the content of O (oxygen) is d (atomic %), then 1<a<96, 1 <b+c<95, 0<
d<67 (but a<0.25(100-d) and c<
An oxide containing Zr, B, and Si (ZrB_
xSi_zO_y) as the main component, and the atomic ratio x of B to Zr, the atomic ratio z of Si to Zr, and the atomic ratio y of O to Zr are 0.05≦x+z<19 (however, x+z
-3>0 and x-3z+1>0 (excluding the composition of x-3z+1>0) and 2<y<40. (ZrB_
xSi_zO_y, 0.05≦x+z<19 (however, x
+z-3>0 and x-3z+1>0) and 2<y<40). 10, containing at least one of Zr, Ti, Hf, Sn, Ta, and In and at least one of B and Si;
The target for producing an amorphous oxide film according to claim 1. 11. Zr (zirconium) 7 to 91 atom%, B (boron) 3 to 80 atom%, O (oxygen) 0 to 67 atom%
A target whose main component is a substance that contains it. 12, Zr (zirconium) 1 to 96 atomic%. Si (silicon): 1 to 95 atomic%, O (oxygen): 0 to 6
A target whose main component is a substance containing 7 atomic percent. 13. The content of Zr (zirconium) is a (atomic %),
The content of B (boron) is b (atomic %), Si (silicon)
When the content of is c (atomic %) and the content of O (oxygen) is d (atomic %), 1<a<96, 1<b+c<95, 0
<d<67 (but a<0.25(100-d) and c
A target whose main component is a substance having a composition of <0.25 (excluding a composition of 100-d).