JPH06112009A - High resistance film and manufacture thereof - Google Patents

Abstract

PURPOSE:To obtain the manufacturing method for a high resistance film having the specific resistance value several times higher than that of the conventional Ni-Cr alloy film and also having a practical resistance temperature coefficient. CONSTITUTION:This is the method in which a high resistance film, containing boron of 20 to 80wt.% in transition metal which is at least a kind selected from Cr, Mo, Nb, Ta, Ti, W and Zr, is formed on a substrate by evaporating the transition metal and boron simultaneously from the independent sources of evaporation respectively by changing the amount of evaporation.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high resistance film and a method of manufacturing the high resistance film, and more particularly to a high resistance film used for a thin film resistor and a heating resistor of a thermal head and a method of manufacturing the same.

[0002]

2. Description of the Related Art Conventionally, Ni-Cr and the like have been known as resistance materials for thin film resistors, and Cr-Si-O and Ta-Si- as heat-generating resistor materials for thermal heads.
O etc. are known.

[0003]

In recent years, a resistance material having a larger specific resistance and a smaller temperature coefficient of resistance (TCR) has been demanded due to the demand for miniaturization and high integration of electronic parts.

However, the specific resistance of Ni-Cr used as the resistance material of the thin film resistor is 100 μΩcm.
Since it is as small as (0.1 mΩcm), it is necessary to reduce the film thickness or make the pattern fine in order to obtain high resistance.
However, when the film thickness is 200 Å or less, the resistance value is likely to be unstable, which makes it difficult to manufacture a fine pattern and also deteriorates the high frequency characteristics.

Further, Cr-Si-O or Ta-Si used as a heating resistor material of a thermal head.
-O has a problem that the resistance value changes greatly even if the oxygen concentration in the film changes slightly.

The present invention solves the above-mentioned conventional problems, and
It is an object of the present invention to provide a high resistance film having a specific resistance that is 5 times or more that of i-Cr and a practical temperature coefficient of resistance, and a manufacturing method thereof.

[0007]

The high resistance film of the present invention is a film manufactured by the following method.

(1) A vacuum atmosphere, a gas atmosphere containing a nitrogen component, or a gas atmosphere containing a carbon component by any one of a vacuum vapor deposition method, an activated reactive vapor deposition method, an ion plating method, and a CVD method. In a medium or in a gas atmosphere containing a mixed component of nitrogen and carbon, a transition metal or an alloy containing a transition metal element and boron are simultaneously evaporated from independent evaporation sources at arbitrary evaporation rates, and Cr, M
20-80 boron in at least one transition metal selected from the group consisting of o, Nb, Ta, Ti, W, Zr.
A high resistance film formed with an alloy film containing wt%. Alternatively, Cr, Mo, Nb, Ta, T containing 0 to 50 at% of any one of nitrogen, carbon, and a mixed element of nitrogen and carbon on the substrate.
It is a high resistance film in which an alloy film containing 5 to 60 wt% of boron in at least one transition metal selected from the group consisting of i, W and Zr is formed.

(2) The transition metal of (1) above, namely Cr, Mo,
Using a target prepared by mixing boron with an arbitrary composition containing at least one transition metal or a transition metal element selected from the group consisting of Nb, Ta, Ti, W, and Zr, nitrogen is produced by sputtering. In a gas atmosphere containing a component, or in a gas atmosphere containing a carbon component, or in the gas atmosphere containing a mixed component of nitrogen and carbon on the target sputtering alloy film of the composition of (1) above,
That is, an alloy film containing 20 to 80 wt% of boron in at least one transition metal selected from the group consisting of Cr, Mo, Nb, Ta, Ti, W and Zr, or nitrogen, carbon,
0-5 for any one of the mixed elements of nitrogen and carbon
It is a high resistance film in which an alloy film containing 5 to 60 wt% of boron in at least one transition metal selected from the group consisting of Cr, Mo, Nb, Ta, Ti, W and Zr containing 0 at% is formed.

[0010]

The high resistance film having the constitution of the present invention has a resistivity higher than five times that of the Ni-Cr alloy film in the composition range.
Moreover, the high resistance film has a small temperature coefficient of resistance.

[0011]

EXAMPLES Specific examples of the present invention will be described.

Example 1 This example is an example of forming a binary alloy film of B-Cr on a substrate by a vacuum evaporation method.

First, a glass substrate (not shown) is held by a substrate holding device (not shown) provided above the vacuum processing chamber (not shown), and the glass substrate (not shown) is placed below the vacuum processing chamber. Of the pair of evaporation sources (not shown) provided, one evaporation source was filled with chromium (Cr) as a transition metal element, and the other evaporation source was filled with boron (B). Next, the inside of the vacuum processing chamber is set to a vacuum degree of 1 × 10 ⁻⁵ Torr or less, and chromium and boron are respectively heated and evaporated by each evaporation source, and the evaporation amount is variously changed, and chromium is evaporated on the substrate. The amount of boron added to the film, that is, the boron concentration varies from 0.3 to 0.
A binary alloy film composed of 4 μm of B—Cr was formed.

Then, the specific resistance and the temperature coefficient of resistance were measured as the electrical characteristics of each B--Cr alloy film formed on the substrate,
The results are shown in FIG. 1 with the specific resistance as curve A and the temperature coefficient of resistance as curve B. As is clear from FIG. 1, as the concentration of boron increases, a specific resistance value of 5 times or more of the specific resistance value (0.1 mΩcm) of the conventional Ni-Cr alloy is obtained, and the temperature coefficient of resistance of boron is Decreases with increasing concentration,
It was found to have a practical value within ± 500 ppm / K. It is also possible to make the value of the temperature coefficient of resistance almost zero.

Example 2 A binary alloy film made of B-Nb having various boron concentrations was formed on a substrate in the same manner as in Example 1 except that niobium (Nb) was used as the transition metal instead of chromium. When the specific resistance value and the resistance temperature coefficient were measured as the electrical characteristics of each of the formed B-Nb alloy films having different boron concentrations, the specific resistance value was 5 times or more that of Ni-Cr, and the resistance temperature coefficient was Was within ± 500 ppm / K.

Example 3 A binary alloy film made of B-Ti having various boron concentrations was formed on a substrate in the same manner as in Example 1 except that titanium (Ti) was used as the transition metal instead of chromium. Then
When the specific resistance value and the resistance temperature coefficient were measured as electric characteristics for each B-Ti alloy film having different boron concentration, the specific resistance value was 5 times or more that of Ni-Cr, and the resistance temperature coefficient was ± It was within 500 ppm / K.

Example 4 A binary alloy film made of B-Mo having various boron concentrations was formed on a substrate in the same manner as in Example 1 except that molybdenum (Mo) was used as the transition metal instead of chromium. Then, when the specific resistance value and the resistance temperature coefficient were measured as electric characteristics for each of the B-Mo alloy films having different boron concentrations, the specific resistance value was 5 times or more that of Ni-Cr, and the resistance temperature coefficient was It was within ± 500 ppm / K.

Example 5 A binary alloy film made of B-W having various boron concentrations is formed on a substrate in the same manner as in Example 1 except that tungsten (W) is used as the transition metal instead of chromium. Then, when the specific resistance value and the resistance temperature coefficient were measured as electric characteristics for each of the B-W alloy films having different boron concentrations, the specific resistance value was 5 times or more that of Ni-Cr, and the resistance temperature coefficient was It was within ± 500 ppm / K.

Example 6 The same as Example 1 except that the ion plating method by HCD (hollow cathode discharge) method was used instead of the vacuum deposition method as the method for forming the B—Cr alloy film on the substrate. When a binary alloy film made of B-Cr having various boron concentrations was formed by the method described above, and a specific resistance value and a temperature coefficient of resistance were measured as electrical characteristics for each of the B-Cr alloy films having different boron concentrations, The specific resistance value was 5 times or more that of Ni-Cr, and the temperature coefficient of resistance was within ± 500 ppm / K.

Example 7 Example 1 was repeated except that a CVD method using B ₂ H ₆ and TiCl ₄ as source gases was used instead of the vacuum deposition method as a method for forming the B—Ti alloy film on the substrate. A binary alloy film composed of B-Ti having different boron concentrations was formed by the same method as described above, and the specific resistance value and the resistance temperature coefficient were measured as the electrical characteristics of each B-Ti alloy film having different boron concentrations. However, the specific resistance value is 5 times or more that of Ni-Cr,
The temperature coefficient of resistance was within ± 500 ppm / K.

Example 8 In this example, B-Cr was formed on a substrate by activation reactive vapor deposition.
It is an example of forming a ternary alloy film of -C.

First, a glass substrate (not shown) is held by a substrate holding device (not shown) provided above the vacuum processing chamber (not shown), and is placed below the vacuum processing chamber. Of the pair of evaporation sources (not shown) provided, one evaporation source was filled with chromium (Cr) as a transition metal, and the other evaporation source was filled with boron (B). Next, the degree of vacuum in the vacuum processing chamber is set to 1 × 10 ⁻⁵ Torr or less, and then C ₂ H ₂ gas is introduced as a carbon component so that the inside of the vacuum processing chamber becomes 4 × 10 ⁻⁴ Torr. The atmosphere.

Then, chromium and boron are respectively heated and vaporized by each evaporation source, and the vaporization amount is variously changed and vapor-deposited on the substrate so that the carbon content in chromium is 50 at%.
In addition, the film thickness of boron having various concentrations of boron to chromium is 0.
A ternary alloy film of B-Cr-C having a thickness of 4 to 0.5 μm was formed.

Then, each B-Cr-C formed on the substrate
As the electrical characteristics of the alloy film, the specific resistance value and the temperature coefficient of resistance were measured, and the results are shown in FIG. 2 as curve C for resistance and curve D for resistance temperature coefficient. As is clear from FIG. 2, as the concentration of boron increases, a specific resistance value of 5 times or more of the specific resistance value (0.1 mΩcm) of the conventional Ni-Cr alloy is obtained, and the temperature coefficient of resistance of boron is Decreases with increasing concentration,
It was found to have a practical value within ± 500 ppm / K. Further, it is possible to set the value of the temperature coefficient of resistance to substantially zero as in the first embodiment.

Example 9 B was used in the same manner as in Example 8 except that the amount of carbon in chromium was changed to 20 at% and 40 at%, and the concentration of boron was varied.
A ternary alloy film made of -Cr-C was formed.

When the specific resistance value and the temperature coefficient of resistance were measured as the electrical characteristics of each B-Cr-C alloy film, the specific resistance value of each B-Cr-C alloy film was 5 times that of Ni-Cr or more. And the temperature coefficient of resistance is B-Cr-
The C alloy film was also within ± 500 ppm / K.

Example 10 In this example, B-Ti was formed on a substrate by an activated reactive vapor deposition method.
It is an example of forming a ternary alloy film of -C.

The amount of carbon in titanium deposited on the substrate was 50 at% by the same method as in Example 8 except that titanium (Ti) was used as the transition metal instead of chromium.
In addition, the film thickness of boron having various concentrations of boron with respect to titanium is 0.
A ternary alloy film of B-Ti-C having a thickness of 5 to 0.7 μm was formed.

Then, each B-Ti-C formed on the substrate
As the electrical characteristics of the alloy film, the specific resistance value and the temperature coefficient of resistance were measured, and the results are shown in FIG. As is clear from FIG. 3, with the increase of the concentration of boron, the specific resistance value of the conventional Ni-Cr alloy is more than 7 times (0.1 mΩcm), and the temperature coefficient of resistance of boron is Decreases with increasing concentration,
It was found to have a practical value within ± 500 ppm / K. Further, it is possible to set the value of the temperature coefficient of resistance to substantially zero as in the first embodiment.

Example 11 In this example, B-Ti was formed on a substrate by an activated reactive vapor deposition method.
This is an example of forming a quaternary alloy film of -CN.

First, a glass substrate (not shown) is held by a substrate holding device (not shown) provided above the vacuum processing chamber (not shown), and the glass substrate is placed below the vacuum processing chamber. Of the pair of evaporation sources (not shown) provided, one evaporation source was filled with titanium (Ti) as a transition metal, and the other evaporation source was filled with boron (B). Next, the degree of vacuum in the vacuum processing chamber is set to 1 × 10 ⁻⁵ Torr or less, and then C ₂ H ₂ gas as a carbon component and N as a nitrogen component so that the vacuum processing chamber has a pressure of 4 × 10 ⁻⁴ Torr. _Two gases were introduced to make a mixed gas atmosphere of carbon and nitrogen (partial pressure 1: 1).

Subsequently, titanium and boron are respectively heated and vaporized by the respective evaporation sources, and while varying the vaporization amount, vapor deposition is carried out on the substrate so that the carbon content in titanium is 25 at% and the nitrogen content is 25 at%. B-Ti-C-N having a film thickness of 0.5 to 0.6 μm and having various boron concentrations relative to titanium
Was formed of a quaternary alloy film.

Then, each B-Ti-C formed on the substrate
A specific resistance value and a temperature coefficient of resistance were measured as electrical characteristics of the -N alloy film, and the results are shown in FIG. 4 as a curve G of a specific resistance and a curve H of a resistance temperature coefficient. As is clear from FIG.
With the increase of the boron concentration, the specific resistance value more than 5 times the specific resistance value (0.1 mΩcm) of the conventional Ni-Cr alloy was obtained, and the temperature coefficient of resistance decreased with the increase of the boron concentration, It was found to have a practical value within 500 ppm / K. Further, it is possible to set the value of the temperature coefficient of resistance to substantially zero as in the first embodiment.

Example 12 In this example, B-Ti was formed on a substrate by an activated reactive vapor deposition method.
It is an example of forming a ternary alloy film of -N.

Titanium (Ti) is used as the transition metal instead of chromium, and the atmosphere in the vacuum processing chamber at the time of forming the alloy film is N ₂ as the nitrogen component instead of the carbon gas atmosphere.
The amount of nitrogen in chromium deposited on the substrate was 50 at% by the same method as in Example 9 except that a gas was introduced and the pressure in the vacuum processing chamber was set to a nitrogen gas atmosphere of 4 × 10 ⁻⁴ Torr. A ternary alloy film made of B-Ti-N having a film thickness of 0.6 to 0.7 μm and having various boron concentrations relative to titanium was formed.

Then, each B-Ti-N formed on the substrate
The specific resistance value and the temperature coefficient of resistance were measured as the electrical characteristics of the alloy film, and the results are shown in FIG. As is clear from FIG. 5, as the concentration of boron increases, a specific resistance value of 5 times or more of the specific resistance value (0.1 mΩcm) of the conventional Ni—Cr alloy is obtained, and the temperature coefficient of resistance of boron is Decreases with increasing concentration,
It was found to have a practical value within ± 500 ppm / K. Further, it is possible to set the value of the temperature coefficient of resistance to substantially zero as in the first embodiment.

Example 13 In this example, B-Zr was formed on a substrate by an activated reactive vapor deposition method.
It is an example of forming a ternary alloy film of -N.

Zirconium (Zr) was used as the transition metal instead of chromium, and N ₂ gas was introduced as the nitrogen component instead of the carbon gas atmosphere in the vacuum processing chamber when the alloy film was formed. Pressure is 4 × 10 ^-4 Tor
The amount of nitrogen in zirconium deposited on the substrate was 50 in the same manner as in Example 9 except that a nitrogen gas atmosphere of r was used.
A ternary alloy film made of B-Zr-N having a film thickness of 0.4 to 0.5 [mu] m, which is at% and has a different boron concentration with respect to zirconium, was formed.

Then, each B-Zr-N formed on the substrate
As the electrical characteristics of the alloy film, the specific resistance value and the temperature coefficient of resistance were measured, and the results are shown in FIG. As is clear from FIG. 6, with the increase of the boron concentration, the specific resistance value of 5 times or more of the specific resistance value (0.1 mΩcm) of the conventional Ni—Cr alloy was obtained, and the temperature coefficient of resistance of boron was Decreases with increasing concentration,
It was found to have a practical value within ± 500 ppm / K. Further, it is possible to set the value of the temperature coefficient of resistance to substantially zero as in the first embodiment.

Example 14 In this example, an alloy target of chromium and boron is used and a binary alloy film made of B—Cr is formed on a substrate by a sputtering method.

First, a glass substrate (not shown) is held by a substrate holding device (not shown) provided above the vacuum processing chamber (not shown), and the glass substrate is placed below the vacuum processing chamber. Chromium (Cr), boron (B), 30 wt%, 40 wt% and 50 wt% on the RF magnetron cathode (not shown).
Either of the% doped target materials was placed. Next, the degree of vacuum in the vacuum processing chamber was set to 1 × 10 ⁻⁵ Torr or less, and subsequently, argon gas was introduced so that the vacuum processing chamber became about 1 × 10 ⁻³ Torr. Subsequently, the target materials having different boron contents were sputtered by the RF magnetron sputtering method to form a binary alloy film made of B-Cr having a film thickness of 0.5 μm with various boron concentrations on chromium on the substrate.

Then, when the specific resistance value and the temperature coefficient of resistance were measured as the electric characteristics of each B—Cr alloy film formed on the substrate, the specific resistance value was 5 times or more that of Ni—Cr.
The temperature coefficient of resistance was within ± 500 ppm / K.

Example 15 In this example, an alloy target of titanium and boron was used, and B-Ti- was formed on the substrate by sputtering in a nitrogen gas atmosphere.
This is an example of forming a ternary alloy film of N. First, a glass substrate (not shown) is held in a substrate holding device (not shown) arranged above in a vacuum processing chamber (not shown),
A target material in which titanium (Ti) was doped with 10 wt%, 20 wt% or 30 wt% of boron (B) was placed on an RF magnetron cathode (not shown) arranged below the vacuum processing chamber. Next, the vacuum degree in the vacuum processing chamber is 1
× 10 ^-5 Torr or less, then 1 × in the vacuum processing chamber
Argon gas and N ₂ gas as a nitrogen component were introduced so as to obtain 10 ⁻³ Torr to make a nitrogen gas atmosphere.

Subsequently, the target materials having different boron contents were sputtered by the RF magnetron sputtering method, the nitrogen in the titanium was 50 at% on the substrate, and the boron concentration relative to the titanium was varied. A ternary alloy film of B-Ti-N having a thickness of 0.5 μm was formed.

Then, each B--Ti-- formed on the substrate
When the specific resistance value and the resistance temperature coefficient were measured as the electrical characteristics of the N alloy film, the specific resistance value was 5 times or more that of Ni-Cr, and the resistance temperature coefficient was within ± 500 ppm / K.

The manufacturing method of the high resistance film of the present invention is not limited to the above-mentioned embodiment, but Cr, Mo, Nb, T may be used.
When a high resistance film containing 20 to 80 wt% of boron in at least one transition metal of a, Ti, W, and Zr is formed on a substrate, a vacuum deposition method, an activated reactive deposition method, an ion plating method. Method, CVD method, or sputtering method is selected, and among these methods, the transition metal and boron are evaporated by heating while changing the evaporation amount respectively,
Alternatively, by performing sputtering on targets having different boron contents, it is possible to form a high resistance film in which boron is formed in the transition metal at an arbitrary mixing ratio.

At least one transition of Cr, Mo, Nb, Ta, Ti, W, and Zr containing any one of nitrogen, carbon, and a mixed element of nitrogen and carbon in the range of 0 to 50 at%. When forming a high resistance film in which boron is contained in the metal in an amount of 5 to 60 wt% on the substrate, nitrogen gas, carbon gas alone or mixed gas is introduced during the film formation, or nitrogen gas in a plasma atmosphere, A high resistance film in which carbon, nitrogen, or any one of the mixed elements of carbon and nitrogen and boron are composed in an arbitrary mixing ratio is formed in the transition metal by introducing a single gas or a mixed gas of carbon gas. You can do it.

There are various uses of the high resistance film of the present invention. Typical examples thereof are a thin film resistor and a heating resistor of a thermal head.

[0049]

As described above, according to the high resistance film of the present invention, since it has a large specific resistance value which is more than 5 times that of the conventional Ni-Cr alloy film and a practical temperature coefficient of resistance, the specific resistance is high. Since the temperature coefficient of resistance is small, there is an effect that electronic components can be downsized and highly integrated.

Further, according to the method of manufacturing a high resistance film of the present invention, there is an effect that a high resistance film having a high specific resistance and a small resistance temperature coefficient can be manufactured very easily.

[Brief description of drawings]

FIG. 1 is a characteristic diagram showing a relationship between B concentration in a B—Cr film and electrical characteristics,

FIG. 2 is a characteristic diagram showing a relationship between B concentration in a B—Cr—C film and electrical characteristics,

FIG. 3 is a characteristic diagram showing a relationship between B concentration in a B—Ti—C film and electrical characteristics,

FIG. 4 is a characteristic diagram showing a relationship between B concentration in a B—Ti—C—N film and electrical characteristics,

FIG. 5 is a characteristic diagram showing a relationship between B concentration in a B-Ti-N film and electrical characteristics,

FIG. 6 is a characteristic diagram showing the relationship between B concentration in a B-Zr-n film and electrical characteristics.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical indication location H01C 17/08 8834-5E (72) Inventor Konosuke Inagawa 5-9-7 Tokodai, Tsukuba, Ibaraki Japan Sky Technology Co., Ltd. Tsukuba Institute for Supermaterials

Claims (6)

[Claims] 1. Cr, Mo, Nb, Ta, Ti, W, Z
A high resistance film comprising 20 to 80 wt% of boron added to at least one transition metal selected from the group consisting of r. 2. Cr, Mo, N containing 0 to 50 at% of any one of nitrogen, carbon, and a mixed element of nitrogen and carbon.
A high-resistance film comprising 5 to 60 wt% of boron added to at least one transition metal selected from the group consisting of b, Ta, Ti, W, and Zr. 3. Cr, Mo, N from independent evaporation sources
At least one transition metal selected from the group consisting of b, Ta, Ti, W, and Zr and boron are simultaneously vaporized, and any one of vacuum vapor deposition method, activated reactive vapor deposition method, ion plating method, and CVD method is used. Method, Cr, Mo,
20-80 wt% boron in at least one transition metal selected from the group consisting of Nb, Ta, Ti, W and Zr
A method of manufacturing a high resistance film, which comprises forming a high resistance film formed by adding. 4. Cr, Mo, Nb, Ta, Ti, W, Z
A target containing at least one transition metal selected from the group consisting of r and boron is used, and the target is sputtered to form Cr, Mo,
20-80 wt% boron in at least one transition metal selected from the group consisting of Nb, Ta, Ti, W and Zr
A method of manufacturing a high resistance film, which comprises forming a high resistance film formed by adding. 5. In a gas atmosphere containing a nitrogen component, a gas atmosphere containing a carbon component, or a gas atmosphere containing a mixed component of nitrogen and carbon, C is supplied from an independent evaporation source.
At least one transition metal selected from the group consisting of r, Mo, Nb, Ta, Ti, W, and Zr and boron are evaporated at the same time, and a vacuum evaporation method, an activated reactive evaporation method, an ion plating method, a CVD method Any one of nitrogen, carbon, or a mixed element of nitrogen and carbon on the substrate by any one of
Cr, Mo, Nb, Ta, T containing 0 to 50 at% of types
A method for producing a high resistance film, which comprises forming a high resistance film by adding 5 to 60 wt% of boron in at least one transition metal selected from the group consisting of i, W and Zr. 6. Cr, Mo, Nb, Ta, T in a gas atmosphere containing a nitrogen component, in a gas atmosphere containing a carbon component, or in a gas atmosphere containing a mixed component of nitrogen and carbon.
A target containing at least one transition metal selected from the group consisting of i, W, and Zr and boron is used, and the target is sputtered by sputtering, and any one of nitrogen, carbon, and a mixed element of nitrogen and carbon is formed on the substrate. Cr, Mo, Nb, Ta, Ti, which contains 1 to 50 at%
A method for producing a high resistance film, which comprises forming a high resistance film by adding 5 to 60 wt% of boron in at least one transition metal selected from the group consisting of W and Zr.