JP4585952B2 - Thin film made of Ag-based alloy - Google Patents

Description

  The present invention relates to a sputtering target material or vapor deposition material composed of an Ag-based alloy, a reflective film composed of an Ag-based alloy with improved heat resistance while maintaining high reflectivity and low electrical resistance, a thin film for wiring or electrodes, and Ag. The present invention relates to a semi-reflective semi-transmissive film made of a base alloy and having a thickness of 50 nm or less.

  Reflective films used in optical recording media such as CDs (Compact Discs), reflective films used in liquid crystal display devices, organic EL (Electro luminescence) display devices, wiring films and / or electrode films include: In general, thin films of Al or Al-based alloys are often used.

  A multilayer optical recording medium represented by a double-layer DVD-R DL (Double Layer) has a semi-reflective / semi-transmissive layer below the recording layer for writing and reading. As the semi-reflective / semi-transmissive layer, for example, a thin film of Ag or an Ag-based alloy is used.

  Thin films used for these applications are required to have low electrical resistance and be stable against heat and humidity. Further, when it is used as a reflective film, higher reflectance is also required.

  A thin film made of Al or an Al-based alloy has a certain degree of reflectivity and low electrical resistance, and also has a passive corrosion film on the surface layer, so it has stable corrosion resistance in the air. The Al-based alloy thin film, which is weak against heat and humidity and improved, has a drawback that its electric resistance is higher than that of Al.

  Al and Al-based alloys have a reflectance of 80 to 90% with respect to light having a wavelength of 700 nm, for example, and are not sufficiently satisfactory for applications requiring high reflectance.

  Therefore, it is used for applications requiring low electrical resistance and high reflectivity, for example, reflective films used in organic EL displays and liquid crystal displays, thin films for wiring or electrodes, and optical disk media represented by CD and DVD. It has been proposed to use Ag or an Ag-based alloy having a high reflectivity and a low electric resistance for the reflective film and the semi-reflective semi-transmissive film.

  Color filters are generally used for flat panel displays such as liquid crystal display devices, but some color filters contain halogen, and color filters are disposed on the reflective film, wiring film and / or electrode film. When applying, there is a case where it is heated to around 250 ° C. during the process, and there is a problem that a trace amount of halogen element contained in the color filter is liberated by the heating and reacts with Ag to become cloudy or yellow.

  Also in optical recording media, substrates may be bonded together in the manufacturing process of CDs and DVDs. When halogen is contained in the adhesive used at that time, when exposed to a temperature of about 80 ° C. There is a problem in that free halogen is generated and reacts, and the reflectance is lowered.

  Furthermore, in a multilayer optical recording medium or a semi-reflective liquid crystal display, a semi-reflective semi-transmissive film having a thickness of about 1 to 50 nm that reflects a part of the irradiation light and transmits a part thereof is used. Such a thin film is required to have high stability against heat and humidity.

  The main object of the present invention is to have a high reflectance and a low electrical resistance while suppressing a decrease in reflectance due to reaction with a small amount of free halogen due to heat and improving heat resistance, and also against heat and humidity. It is another object of the present invention to provide a reflective film having a high stability, a thin film for wiring or an electrode and a semi-reflective semi-transmissive film, and a sputtering target material and a vapor deposition material useful for producing such a film.

  As a result of intensive studies to achieve the above-mentioned object, the present inventors have now combined Ag with a specific small amount of Cu, at least one element of Te, Se and P, and 3 to 5 components of Mn. When added and alloyed, the high reflectivity and low electrical resistance of Ag are maintained, while the decrease in reflectivity due to the reaction with a small amount of free halogen due to heat is remarkably suppressed and the heat resistance is remarkably improved. It is possible to obtain a base alloy thin film, and to improve the corrosion resistance by alloying by adding a small amount of at least one of In, Sn, Zn, Au, Pt, Pd, Ru and Ir, and further, Ni, Fe, It has been found that heat resistance is further improved by alloying by adding a small amount of at least one of Bi and Cr, and the present invention has been completed.

  Thus, the present invention comprises an Ag-based alloy containing Ag, Cu, Te, Se, Se, and P and Mn, and Cu is 0.005 to 4.995 mass%, Te, Se, and P. 0.005-2.0 mass% of at least one element and 0.005-3.0 mass% of Mn are contained, and the ratio of Cu / (at least one element of Te and Se) is 0.75 or more. The present invention provides a sputtering target material and a vapor deposition material, a reflective film, a thin film for wiring or an electrode, and a semi-reflective transflective film having a film thickness of 50 nm or less.

  The present invention further comprises a sputtering target material and a vapor deposition material comprising the above Ag-based alloy containing 0.005 to 2.0 mass% of at least one metal selected from In, Sn and Zn, The present invention also provides a reflective film, a wiring or electrode thin film, and a semi-reflective semi-transmissive film having a thickness of 50 nm or less.

  The present invention further comprises a sputtering target material comprising the above Ag-based alloy containing 0.005 to 2.0 mass% of at least one metal selected from Pd, Au, Pt, Ru and Ir. And a vapor deposition material, a reflective film, a thin film for wiring or an electrode, and a semi-reflective semi-transmissive film having a film thickness of 50 nm or less.

  The present invention further includes a sputtering target material and vapor deposition comprising the above Ag-based alloy containing 0.005 to 3.0 mass% of at least one metal selected from Fe, Ni, Bi and Cr. The present invention provides a material, a reflective film, a wiring or electrode thin film, and a semi-reflective semi-transmissive film having a thickness of 50 nm or less.

  In the present invention, furthermore, at least one metal selected from In, Sn, and Zn and at least one metal selected from Pd, Au, Pt, Ru, and Ir are added in a total amount of 0.01 to 4.0 mass%. The present invention provides a sputtering target material and a vapor deposition material comprising the above-described Ag-based alloy, a reflective film, a wiring or electrode thin film, and a semi-reflective transflective film having a thickness of 50 nm or less. .

In the present invention, at least one metal selected from In, Sn, and Zn and at least one metal selected from Fe, Ni, Bi, and Cr are added in a total amount of 0.01-5.
A sputtering target material and vapor deposition material comprising the above-mentioned Ag-based alloy containing 0 mass%, and a reflective film, a thin film for wiring or an electrode, and a semi-reflective transflective film having a film thickness of 50 nm or less It is.

  In the present invention, furthermore, at least one metal selected from Pd, Au, Pt, Ru and Ir and at least one metal selected from Fe, Ni, Bi and Cr in total 0.01 to 5. A sputtering target material and vapor deposition material comprising the above-mentioned Ag-based alloy containing 0 mass%, and a reflective film, a thin film for wiring or an electrode, and a semi-reflective transflective film having a film thickness of 50 nm or less It is.

  The present invention further includes at least one metal selected from In, Sn and Zn, at least one selected from Pd, Au, Pt, Ru and Ir, and at least selected from Fe, Ni, Bi and Cr. Sputtering target material and vapor deposition material comprising the above-mentioned Ag-based alloy containing 0.015 to 7.0 mass% of one kind of metal in total, and a reflective film, wiring or electrode thin film and film thickness A semi-reflective semi-transmissive film having a thickness of 50 nm or less is provided.

  Hereinafter, the present invention will be described in more detail. In this specification, the reflective film, the thin film for wiring or electrode, and the semi-reflective semi-transmissive film are simply referred to as “thin film”.

  The thin film of the present invention is basically a quaternary system in which Ag is used as a base, and an alloy is formed by compounding 3 to 5 components of at least one element of Cu and Te, Se and P, and Mn. Made of an Ag-based alloy of Cu, 0.005 to 4.995 mass%, preferably 0.1 to 2 mass%, and at least one element of Te, Se and P is 0.005 to 2.0 mass%, preferably It contains 0.01 to 1 mass% and 0.005 to 3.0 mass%, preferably 0.01 to 2 mass% of Mn, and the remainder can be substantially Ag and inevitable impurities. When Te and / or Se is used as the element, the ratio of Cu to be added and at least one element of Te and Se: Cu / (at least one element of Te and Se) is 0.75. As mentioned above, it is important that it is preferably in the range of 0.9-2. When the ratio is less than 0.75, generally sufficient heat resistance cannot be obtained, and the reflectance decreases greatly during heating.

  In addition, the total content of the three components of Cu, Te, Se and P and Mn in the thin film of the present invention is generally 0.015 to 9.995 mass%, preferably 0.05 to 2. It can be in the range of 0.0 mass%.

  In the thin film of the present invention, at least one metal element selected from In, Sn and Zn (hereinafter referred to as “Group A metal element”) is further added to the basic quaternary Ag-based alloy component. It can be made of a quinary Ag-based alloy formed by alloying. In this ternary Ag-based alloy, the content of the group A metal element can be 0.005 to 2.0 mass%, preferably 0.1 to 1.5 mass%, respectively. By adding these group A metal elements, the corrosion resistance of the obtained Ag-based alloy can be improved.

The thin film of the present invention further comprises at least one metal element selected from Pd, Au, Pt, Ru and Ir (hereinafter referred to as “B group metal element”) in addition to the quaternary Ag-based alloy component. It can be made of a quinary Ag-based alloy that is added and alloyed. In the ternary Ag-based alloy, the contents of the group B metal elements are 0.005 to 2.0 mass%, preferably Au is 0.01 to 0.8 mass%, and Pd is 0.01 to 1, respectively. 0.5 mass%, Pt may be in the range of 0.01 to 0.8 mass%, Ru may be in the range of 0.01 to 0.5 mass%, and Ir may be in the range of 0.01 to 0.2 mass%. The addition of these group B metal elements can also improve the corrosion resistance of the resulting Ag-based alloy.

  In the thin film of the present invention, at least one metal element selected from Fe, Ni, Bi and Cr (hereinafter referred to as “group C metal element”) is further added to the quaternary Ag-based alloy component. It can be made of an alloyed ternary Ag-based alloy. In this ternary Ag-based alloy, the content of the group C metal element can be in the range of 0.005 to 3.0 mass%, preferably 0.01 to 2.0 mass%, respectively. By adding these C group metal elements, the heat resistance of the resulting Ag-based alloy can be further improved.

  The thin film of the present invention may also be composed of a ternary Ag-based alloy obtained by alloying the quaternary Ag-based alloy component by adding both a group A metal element and a group B metal element. it can. In this hexanary Ag-based alloy, the content of the group A metal element can be 0.005 to 2.0 mass%, preferably 0.01 to 1.5 mass%, respectively. The B group metal element content is 0.005 to 2.0 mass%, preferably 0.01 to 0.8 mass% for Au, 0.1 to 1.5 mass% for Pd, and 0. 01 to 0.8 mass%, Ru can be 0.01 to 0.5 mass%, and Ir can be 0.01 to 0.2 mass%. By simultaneously adding both the group A metal element and the group B metal element, the corrosion resistance of the resulting Ag-based alloy can be further improved.

  The thin film of the present invention can also be composed of a hex-based Ag-based alloy obtained by alloying the above-described quaternary Ag-based alloy component by adding both a group A metal element and a group C metal element. In this hexanary Ag-based alloy, the content of the group A metal element can be 0.005 to 2.0 mass%, preferably 0.01 to 1.5 mass%, respectively. The contents of the group C metal elements can be 0.005 to 3.0 mass%, preferably 0.01 to 2.0 mass%, respectively. By simultaneously adding both the group A metal element and the group C metal element, the corrosion resistance of the resulting Ag-based alloy can be improved, and the heat resistance can be further improved.

The thin film according to the present invention may also be composed of a ternary Ag-based alloy obtained by alloying the quaternary Ag-based alloy component by adding both a group B metal element and a group C metal element. it can. In this hex-based Ag-based alloy, the contents of the group B metal elements are 0.005 to 2.0 mass%, preferably Au is 0.01 to 0.8 mass%, and Pd is 0.01 to 1.5 mass%, Pt can be in the range of 0.01 to 0.8 mass%, Ru can be in the range of 0.01 to 0.5 mass%, and Ir can be in the range of 0.01 to 0.2 mass%. The content of each metal element can be 0.005 to 3.0 mass%, preferably 0.01 to 2.0 mass%. By simultaneously adding both the group B metal element and the group C metal element, the corrosion resistance of the resulting Ag-based alloy can be improved, and the heat resistance can be further improved.

The thin film of the present invention is a ternary Ag obtained by alloying the quaternary Ag-based alloy component by further adding three elements of a group A metal element, a group B metal element, and a group C metal element. It can consist of a base alloy. In the ternary Ag-based alloy, the content of the group A metal element can be 0.005 to 2.0 mass%, preferably 0.01 to 1.5 mass%, respectively. The group metal element content is 0.005 to 2.0 mass%, preferably 0.01 to 0.8 mass% for Au, 0.01 to 1.5 mass% for Pd, and 0.01 to 0 for Pt. 0.8 mass%, Ru may be in the range of 0.01 to 0.5 mass%, and Ir may be in the range of 0.01 to 0.2 mass%, and the content of the group C metal element may be 0.005 to 0.005%, respectively. It can be in the range of 3.0 mass%, preferably 0.01 to 2.0 mass%. Thus, the corrosion resistance and heat resistance of the obtained Ag-based alloy can be remarkably improved by simultaneously adding the A group metal element, the B group metal element, and the C group metal element.

  The Ag-based alloy according to the present invention is prepared by a method known per se, for example, Cu and Te, at least one element of Se and P, and Mn are added to Ag in the above amounts, or Cu and Te and Se are added to Ag. And at least one element selected from the group consisting of M and a group A metal element, a group B metal element, or a group C metal element in the above amounts, or at least one of Cu, Te, Se and P to Ag. Species element and Mn, and further add two components of A group metal element and B group metal element, A group metal element and C group metal element or B group metal element and C group metal element in the above amounts, or to Ag At least one element of Cu and Te, Se and P, Mn, and further three components of Group A metal element, Group B metal element and Group C metal element are added in the above amounts to prepare a raw material blend, The gas furnace, high It can be produced by melting at a temperature of from about 1000 to about 1200 ° C. in a suitable metal melting furnace such as a wave melting furnace. As the furnace atmosphere at the time of melting, air is usually used, but an inert gas atmosphere or a vacuum can be used if necessary. In addition, the above Ag-based alloy in a molten state is poured into a suitable mold or the raw material composition is sintered to produce an ingot, which is then forged, and the forged ingot is cold or hot as necessary. After being rolled into a plate shape, the sputtering target material or vapor deposition material of the present invention can be produced by cutting to a predetermined size. The sputtering target material or vapor deposition material of the present invention can also be produced, for example, by putting the raw material mixture prepared as described above into a mold and sintering it by a hot press method, HIP method or the like. .

  As Ag used as the main raw material, those commercially available in the form of powder, granules, plates, lumps and the like can be used, and the purity is usually 99.95% or more, preferably 99.95%. 99% or more is preferred. Further, as additive elements such as Cu, Te, Se, P, In, Sn, Zn, Au, Pd, Pt, Ru, Ir, Ni, Fe, Bi, and Cr, powder, granule, plate, lump, etc. A commercially available product having a purity of 99.9% or more, preferably 99.95% or more is suitable.

  The thin film of the present invention is formed on a suitable substrate by, for example, sputtering target material formed as described above by a known sputtering method such as radio frequency (RF) sputtering method, direct current (DC) sputtering method or the like. It can be produced by sputtering and forming a film.

  In the thin film of the present invention, for example, a sputtering target material serving as a base is manufactured, and another bulk chip made of one or a plurality of other additive metal elements is manufactured, so that the bulk chip has a predetermined composition. The composite sputtering target material is prepared by placing or embedding it on the base sputtering target material, and the composite target material is sputtered on the substrate as described above to form a film. It can also be produced.

  Alternatively, the thin film of the present invention comprises, for example, evaporating or sublimating a vapor deposition material such as a melting ingot or press-molded body of the raw material mixture with an electron beam or the like, and depositing and solidifying on the substrate to produce the thin film. It can also be produced by vapor deposition.

  The thin film of the present invention is further formed by, for example, depositing an Ag-based alloy on a suitable substrate by vapor deposition or the like according to a method known per se using an ingot or plate made of an Ag-based alloy obtained as described above. Can also be produced.

The semi-reflective transflective film having a film thickness of 50 nm or less, preferably 1 to 30 nm is formed by controlling the sputtering or vapor deposition time or output in the above-described sputtering method or vapor deposition method. It can be produced by controlling the thickness of the film.

  In addition, the production of the wiring film or the electrode film from the thin film of the present invention can be performed, for example, by combining the above-described sputtering method or vapor deposition method with a photoetching method or a photomask method.

  The thin film composed of the Ag-based alloy thus obtained has markedly improved heat resistance and halogen resistance compared to conventional Ag while maintaining the high reflectivity and low electrical resistance inherent in Ag.

Therefore, the thin film composed of the Ag-based alloy of the present invention is, for example, a reflective film of an optical disc medium represented by CD or DVD that requires high reflectivity, a liquid crystal display device, an organic EL display device, As a reflective film, a wiring film or an electrode film, further for a semi-reflective liquid crystal display device or a multilayer optical recording medium, or also a double-layer DVD-R DL (Double)
It can be advantageously used as a semi-reflective / semi-transmissive layer of a multilayer optical recording medium represented by Layer).

  Hereinafter, the present invention will be described more specifically with reference to examples.

Add 0.595 mass% Cu and 0.595 mass% Te, or 0.68 mass% Cu and 0.12 mass% P to Ag, and melt and cast in a gas furnace to produce an ingot. Hot forging was performed, the forged ingot was hot or cold rolled, rolled to a predetermined thickness, and then cut to φ4 inches to produce a sputtering target material. Further, for comparison, only Ag was processed in the same manner as described above to produce an Ag target material.
Table 1 shows the elemental analysis values of the produced sputtering target material.

One or more bulk chips shown in Table 2 in a predetermined amount were placed on the above sputtering target material to produce a composite target material according to the present invention. Further, a Mn chip, a 50 mass% Cu-50 mass% Te alloy chip, or a 50 mass% Cu-50 mass% Mn alloy chip was placed on the Ag target material to produce a composite target material of a comparative example. An Ag target material or a composite target material was formed on a glass plate by a radio frequency (RF) sputtering method so as to have a film thickness of 200 nm, and thin film samples for examples (sample Nos. 1-1 to 1-15) and Thin film samples for comparison (Sample Nos. 1-1 to 1-4) were produced. A part of each thin film sample was taken, the thin film on the glass substrate was made into a solution with nitric acid or the like, and analyzed with an ICP emission spectroscopic analyzer. The results are shown in Table 3.

  In the above, in addition to the thin film sample prepared for analysis, a thin film sample having a film thickness of 130 nm was simultaneously manufactured for the performance test without moving the position of the target material.

  The analysis value of the composition of the produced thin film sample is as shown in Table 3 above, and the reflectance of the produced thin film sample is 95% or more in the wavelength region of 600 to 700 nm in both Examples and Comparative Examples. there were.

Halogen resistance test

After measuring the reflectance of each thin film sample (thickness 130 nm), it was immersed in a supersaturated NaCl aqueous solution for 2 to 3 seconds, taken out and dried with a hot air dryer, and NaCl was deposited on the thin film in a film form at 80 ° C. After the heat treatment for 1 hour, it was washed with water to remove the NaCl film, dried, the reflectance was measured again, and the change rate of the reflectance before and after the treatment was calculated by the following formula (1). As the reflectance, an absolute reflectance value at an incident angle of 5 ° was used. The results are shown in Table 4.
Rate of change (%) = 100- (reflectance after test / reflectivity before test × 100) (1)

  In addition, in order to test the halogen resistance of the semi-reflective semi-transmissive film, a thin film sample having a film thickness of 20 nm was prepared without moving the position of the target material in the same manner as described above.

After measuring the reflectance and transmittance of each thin film sample (film thickness 20 nm), it was immersed in a supersaturated NaCl aqueous solution for 2 to 3 seconds, taken out and dried by a hot air dryer, and NaCl was deposited on the thin film in a film form. After heat treatment at 0 ° C. for 1 hour, the film was washed with water to remove the NaCl film, dried, the reflectance and the reflectance were measured again, and the change rate of the reflectance and transmittance before and after the treatment was calculated by the following formula (2). . As the reflectance, an absolute reflectance value at an incident angle of 5 ° was used. The results are shown in Table 5.
Reflectance and transmittance change rate (%) =
[[100- (Reflectance after test / Reflectivity before test) × 100 ] ² ] ^1/2
+ [[100- (transmittance after test / transmittance before test) × 100 ] ² ] ^1/2 (2)

As a method for simply evaluating the influence of both free halogen and heat, after measuring the reflectance of each thin film sample (film thickness 130 nm), it was immersed in a 20% KI aqueous solution for 2 to 3 seconds, washed with water and dried. After heat treatment at 250 ° C. for 1 hour, the reflectance was measured again, and the change rate of the reflectance was calculated by the above formula (1). As the reflectance, an absolute reflectance value at an incident angle of 5 ° was used. The results are shown in Table 6.

  According to the results shown in Tables 4 to 6, the thin film produced from the sputtering target material or vapor deposition material of the present invention represented by Examples 1-1 to 1-15 exhibits excellent halogen resistance, It can be seen that it has excellent halogen resistance even under heating.

Claims (6)

Ag, Cu and Te, Ri name of at least one element and Mn Se and P, the rest consists of inevitable impurities der Ru Ag based alloy, a Cu 0.1 to 2 mass%, Te, Se and P Cu / ( at least one of Te and Se) containing at least one element of 0.01 to 1 mass% and Mn of 0.01 to 2 mass% and containing at least one element of Te and Se A reflection film having a ratio of ( element) to 0.9-2 . It is made of at least one element selected from Ag, Cu, Te, Se, and P, and at least one metal selected from Mn, In, Sn, and Zn, and the rest is made of an Ag-based alloy that is an inevitable impurity. 1 to 2 mass%, at least one element of Te, Se and P is 0.01 to 1 mass%, Mn is 0.01 to 2 mass%, and at least one metal selected from In, Sn and Zn is 0.1 -1.5 mass% and when containing at least one element of Te and Se, the ratio of Cu / (at least one element of Te and Se) is 0.9-2 Reflective film . It is composed of at least one element selected from Ag, Cu and Te, Se and P, and Mn and at least one metal selected from Pd, Au, Pt, Ru and Ir, and the rest is composed of an Ag-based alloy which is an inevitable impurity. 0.1 to 2 mass% of Cu, 0.01 to 1 mass% of at least one element of Te, Se and P, 0.01 to 2 mass% of Mn, 0.01 to 0.8 mass% of Au, and Pd 0.01-1.5 mass%, Pt 0.01-0.8 mass%, Ru 0.01-0.5 mass% or Ir 0.01-0.2 mass%, and at least one of Te and Se A reflective film characterized in that the ratio of Cu / (at least one element of Te and Se) is 0.9 to 2 when it contains a seed element. At least one element selected from Ag, Cu, Te, Se, and P, and at least one metal selected from Mn, Fe, Ni, Bi, and Cr, and the remainder is made of an Ag-based alloy that is an inevitable impurity. 0.1-2 mass%, at least one element of Te, Se and P is 0.01-1 mass%, Mn is 0.01-2 mass%, and at least one metal selected from Fe, Ni, Bi and Cr Is 0.01 to 2 mass% and contains at least one element of Te and Se, the ratio of Cu / (at least one element of Te and Se) is 0.9 to 2 Reflective film. A thin film for wiring or an electrode comprising the Ag-based alloy according to any one of claims 1 to 4 . A semi-reflective transflective film having a film thickness of 50 nm or less made of the Ag-based alloy according to any one of claims 1 to 4 .