TW201142058A - Bi-ge-o sintered sputtering target, manufacturing method therefor, and optical recording medium - Google Patents

Abstract

Provided are: a sintered target comprising bismuth (Bi), germanium (Ge), and oxygen (O); a manufacturing method therefor; and an optical recording medium. Said Bi-Ge-O sintered sputtering target is characterized in that the relationship between the number of bismuth atoms and the number of germanium atoms satisfies the relation 0.57 < (Bi/(Bi+Ge)) 12GeO20, Bi4Ge3O12, and GeO2. The provided target does not crack upon sputtering, generates few particulates, allows fabrication of stably high-quality thin films, and makes it possible to obtain an optical recording medium with no errors in recorded bits.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a Bi-Ge 0 -based sintered body sputtering target, a method of manufacturing the same, and an optical recording medium, particularly in the case of sputtering. The dry crack 'has a small amount of particles, can stably produce a high-quality film' and obtains an optical recording medium that does not cause recording bit errors.

Bi — Ge — a bismuth sintered body sputtering target, a method of producing the same, and an optical recording medium. [Prior Art] The WORM 'Write Once Read Many' optical recording medium is an optical recording medium that can record the vapor density even if the laser light in the indigo wavelength region (350 to 5 〇〇 nm) is used. In particular, it is an optical recording medium having a high recording sensitivity and having a plurality of recording layers. In order to meet the demand for higher density, the optical disc is being made denser by multi-layering. The development of an optical recording medium for high-density recording is also being carried out in a disc using a blue LD. In order to realize a recordable optical recording medium capable of high-density multi-layer recording, a material having a stable composition and structure is self-evident, and it is also required to have a light-transmissive film which is excellent in oxide film, and is generally an oxide. The point is high, so the sputtering method is often used as a film forming method. Therefore, there is a need for a suitable method for obtaining such a film. 'However, since the form, structure, and the like of the compound constituting the target also affect the sputtering characteristics, whether or not the compound of the koji is suitable for the characteristics of the desired film is stable or not. The problem of sputtering. 201142058 When using a sputtering method to form an optical recording medium with a thin phosphine-shaped yttrium, a ± y * y * waist on the substrate, it may cause a decrease in the quality of the particles due to the material. . Especially in high-recording density media, recording bit errors caused by private cells or the like are serious problems. Therefore, the cause is that the rain is not good, and the yield is reduced. Previously, the proposed optical recording medium was proposed with a variety of materials. For example, Patent Document 1 discloses an optical recording medium in which at least a recording layer is formed on a substrate, and constituent elements of the recording layer are Βι and 0 (oxygen), contain B, and contain a material selected from Ge and u. 1 bn, Cu, Fe, Pd,

At least one element x of Zn, Mg, Nd, Mn, Ni. Further, Patent Document 2 describes an optical recording medium of a type of tracking type, which is characterized in that the recording layer contains Bi and M (MA 1U 〇 a horse, Cr Cr Cr, Μη, Co,

Fe, Cu, Zn, Li, Si 'Ge, Zr, Ti, Hf c 11 Hf, Sn, Mo, V, Nb, m at least one element) and oxygen 'recording mark portion containing information includes the recording layer Crystals of the elements contained and/or crystals of oxides of the elements. In addition, it is also proposed to have patents! 1 Kui 』 also offers 3 ~ Patent Document 8. Among these, a combination of an optical recording medium composed of bismuth (Bi), bismuth (Ge), oxygen ((1) sergeant, and milk (0) is also considered, and a sintered body is also described. ^. The sputtering of the target is formed to form the optical recording medium. J, the so-called B i — (} e 〇彡, g $ υ糸 sintered sputtering target has the following problems: the thermal shock is weak, and the high Power Push&gt; When the door force advances and splashes, cracks and cracks often occur, which leads to the occurrence of particles, and the quality of the recording film of Shanghai. The patent document 1: Japanese wood pq 1 Λ Λ η Japanese Patent Publication No. 2008-210492 Patent Document 2: Japanese Oysters ο λ λ γ 特 2006 2006 1 420 420 420 420 420 420 420 420 420 420 420 420 420 420 420 420 420 420 420 420 420 420 420 420 420 420 420 420 420 420 420 420 420 420 420 420 420 420 — — — — — — — Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. SUMMARY OF THE INVENTION The subject of the present invention is related to a Bi-Ge_〇 In particular, the present invention provides a method for producing a target, a method for producing the target, and an optical recording medium, and in particular, provides a film which does not cause cracks and particle generation when the key is extinguished, and can stably produce a high-quality film without obtaining a high-quality film. In the optical recording medium of the optical recording medium in which the bit error is recorded, the bismuth-based sintered body sputtering target, the method for producing the target, and the optical recording medium have been developed. The inventors of the present invention have conducted intensive studies to obtain the following results. Knowledge insight: Bi-^- 〇-based sintered body of appropriate composition can be selected to control the crystal phase, suppress the thermal shock of the target and prevent the crack of the target, and can effectively suppress the generation of particles during sputtering. The present invention provides: U a Bi-Ge-lanthanum sintered body sputtering target composed of bismuth (Bi), bismuth (Ge), and milk (〇), characterized in that: (1) the atomic ratio is 〇-57&lt;(Bl/(Bi+Ge))&lt;〇92, containing Bii2Ge〇2〇, Bi4Ge3〇2

A three-phase phase of Ge〇1 is used as a crystal phase; and a sintered body sputtering target of the above-mentioned 丨), wherein 2〇〇 is applied to the crucible. (:, 3 minutes of thermal shock during heating, the average bending strength before and after the thermal shock is 201142058, the low rate is less than 50%; 3) - an optical recording medium, which is carried out using the above 丨) or 2): Formed from antimony ore. Further, the present invention provides: '4) A method for producing a Bi-Ge-lanthanum sintered body sputtering target, characterized in that: Ge02 powder 〇.3~89 mol% 'Bil2Ge02G powder π~99_97 mol% is used as a starting material After mixing the raw materials in such a manner that the atomic ratio of Bi to Ge is 〇57 &lt;(Bi/(Bi+Ge))&lt;0.92, hot pressing is carried out at ~840 ° C under a pressing pressure of 150 to 400 kg/cm 2 . Thus, a sintered body containing a crystal phase of three phases of BiuGeOu, BUGe^Ou, and Ge〇2 is produced; 5) A method for producing a Bi-Ge-lanthanum sintered body sputtering target as described in 4) above, in which 'mixed Ge 12 powder 14.3mol% and other 2〇3 powder 85 7m〇i%, then solid phase reaction to produce Bil2GeO20 powder; 6) Bi-Ge- Ο sintered body sputtering target as in 4) or 5) above In the production method, sintering is performed using a sintered raw material powder of cerium oxide having an average crystal grain size of 10 to 5 Å/m. The Bi-Ge-bismuth sintered body sputtering target of the present invention has an excellent effect of not causing cracks in the target during sputtering, and the particles m are less generated therein, and a high-quality film can be stably produced and obtained. It does not produce an optical recording medium in which I玍5 has recorded a 7L bit error. [Embodiment] The Bi-Ge-O sintered body sputtering target of the present invention is composed of germanium (Ge) and oxygen (0), and is characterized in that the atomic ratio of Bi to Ge is a force &lt; (Bi /(Bi+Ge))&lt; 〇.92, containing 3 phases of Bi, 2Ge〇2〇, Bi4Ge3〇2, and Ge〇6 201142058 as a crystal phase. The recording film of this composition is a preferable composition which can achieve high-density recording by multilayering, and can stably perform good sputtering film formation. Λ Generally, a powder of antimony trioxide (Βΐ2〇3) and cerium oxide (Ge〇2) is used as a starting material to sinter the starting material, and when the composition target is produced, it will become a phase of Bi12Ge02G and Bi4Ge3012. Coexistence composition. However, since the difference in thermal expansion coefficient of BkGeO^ is large, the thermal shock of the hairline is extremely weak, and cracking occurs during film formation at high power. In the present invention, the coefficient of thermal expansion is taken between BhGeOw and =4Ge3〇12. The value of Ge 〇 2 is used as an intermediate phase, and it is made into a phase in which the sintered body 3 phase coexists, whereby the 〇 2 phase becomes a buffer phase, and the thermal shock resistance is greatly improved. In addition, the thermal expansion coefficient of Bil2Ge〇2〇 is i 39χΐ〇5, the thermal expansion coefficient of one to two is 6.〇〇χ1〇—on the other hand, the number of sounds is 7.59Χ1 (Γ6, which is the first two) The phase between the thermal expansion coefficient can be used as an effective buffer phase. * The following advantages can be obtained: the thermal shock resistance of the target is obtained (5), thereby forming a film at high power, which can improve production efficiency. : The effect is as follows: the production of particles caused by cracks or cracks is significantly reduced, and can be produced; the film can be produced without recording bits = and the medium can be made. &quot; The light recording is also effective for the particle average particle size of the target. 100//m or less, for the prevention of sputtering 201142058 2. Wide: The m° sintered body of the present invention _ dry, right (four) wide 0 In the case of thermal shock of minute heating, the average bending strength reduction rate before and after the thermal shock is 50% or less. Bi|2GeC&gt;2 of the prior product coexists with Bi4Ge3〇ik 2 phase to form the above-mentioned thermal shock The average bending strength reduction rate before and after is over $(four)' relative to this A large improvement effect is obtained, thereby suppressing dry cracks caused by thermal shock, and directly evaluating m, the ratio of the three phases of the target Bil2Ge〇2Q 'Bi4Ge3〇i2 'Ge〇2 can be used in the present invention. Any adjustment within the scope of the manufacturing conditions. The ratio also depends on the degree of thermal shock of the dry plating during the money plating, that is, the film forming speed (production speed) or the structure of the sputtering device becomes an indicator for mitigating thermal shock. The use of the above-mentioned optical recording medium without sputtering is a stable high-quality 3 film' to obtain an optical recording medium which does not cause recording bit error. When manufacturing a Bi-Ge-yttrium sintered body sputtering In the case of the target, the powder of antimony trioxide and cerium oxide is used as a starting material, and the atomic ratio of (1) and &amp; is 〇.57 &lt;(Bi/(Bi+Ge))&lt;〇%. Then, the mixture is powdered at _~84『c, pressure i 5〇~ under hot pressing. This makes it possible to produce a crystal containing three phases of Bii2Ge〇2〇, called 〇|2 and Ge〇2. The sintered body of the phase. The sintering condition is a preferred condition for obtaining a dry composition of uniform composition. It is preferable to produce &amp; in the range of sintering conditions of the above range, but the reproducibility of the target quality is poor, so it is preferably in the above range. Further, the ratio of the atomic number of 1 in the above-mentioned raw material phase to Ge is 〇57&lt;(Bi/(Bi +Ge"&lt;〇% is directly reflected in the dry, and the composition ratio target can be obtained. 8 201142058 When manufacturing a Bi_Ge-lanthanum sintered body sputtering target, it is preferable to use as a sintering raw material for the third-phase oxidation and emulsification. Use G e 〇Λ λ. and use two powders of 0.03~89mol%,

Bi12GeO20j (^ 11 to 99.97mni〇 / 甘·*·/ m 〇./, is also used to efficiently obtain important conditions including Bi12Ga〇20, Bi4Ge3〇i2 and Ge. The sintered body is preferably sintered by using an oxidized erbium (Ge〇2) powder having an average crystal grain size of 10 to 50 m. The reason is that when the lower limit value is not reached, the agglomeration of the powder is liable to occur, which is difficult. A uniform sintered body is obtained. When the above-mentioned upper limit is exceeded, coarse particles are generated in the dried sintering, and it is easy to segregate. Therefore, it is preferably in the above range. This range is a condition of a better powder, but by The powder can be used in addition to the range. For the Bll2Ge〇20 powder, the solid phase reaction can be carried out after mixing the Ge〇2 powder 14 3 and the β powder with the powder of 85.7 m〇1%. In advance, there is no special limitation on the particle size of B i丨2 Ge Ο 2〇 powder, and there is no special problem as long as it is less than 1〇〇m. It’s in Under the sintering conditions of the present invention, 'there is no agglomeration such as Ge02. Examples Hereinafter, according to The embodiment and the comparative example are described. Furthermore, the present embodiment is merely an example, and the present invention is not limited by the example, and the present invention is limited only by the scope of the patent application (4), and includes variations of the present invention. In addition to the examples (Example 1), the purity of 3N (99_9%) = gasification-cardioin was rolled into a starting material of cerium oxide and cerium oxide powder, and the average particle diameter was prepared in advance to be only 芍12.之Ge〇2 powder and flat 201142058 Bii2Ge02 〇 powder with a uniform particle size of 2〇em, respectively, the Ge02 powder is 83.3mol% and the Bii2GeO20 powder is 16.7mol in such a manner that the atomic ratio of Bi to Ge is 〇_67. After that, the mixture was mixed, and the mixed powder was filled in a carbon mold, and hot pressed at a temperature of 700 ° C and a pressure of 250 kg/cm 2 . Further, in the present embodiment, the above molar ratio was achieved. The method of adding Ge〇2 powder and Bi^GeOzo powder's added ratio is adjusted to be a ratio of GeO250.0 mol% and Bi2〇350.〇mol%, and the ratio is adjusted to 0. The sintered body is finished to be a target, and the relative density is 102% (7.44 g/cm3 at a density of 1%) By the X-ray diffraction measurement of the sintered body was confirmed as Bi12Ge〇20,

Biphase structure of Bi4Ge3〇12 and Ge02. The results are shown in Table i. Next, a thermal shock of heating for 2001 and 30 minutes was applied to the target. Then, the bending test of JIS Standard 1601 was carried out (measured from 5 points at any position in the target, and a test piece having a width of 4 ± 0_1 mm, a height of 3 ± 0.1 mm, and a length of 4 〇 to 5 〇 mm was selected and determined. The average of the measurement results at 5 points), and the average bending strength ratio (rate of reduction of strength) before and after the thermal shock was measured. There is a slight deviation due to the difference in the measurement position, but none of them is less than 5〇%, and the rate of decrease in strength is low. Next, using this target, sputtering was performed at a power of 2 kW. As a result, cracks or cracks did not occur in the target, and the generation of particles was less likely to occur than in the comparative examples described below. As a result, the embodiment of the present invention is a target of good 201142058 which has the following excellent effects: no crack is generated, productivity can be improved, and a high-quality film can be stably produced, and light which does not cause recording bit error can be obtained. Record media. 11 201142058 Average bending strength reduction rate (%) 5 § Ge〇2 particle size (^m) &lt;N (N Bi4Ge3〇i2 〇〇〇〇 crystal phase Bii2Ge〇2〇〇〇〇〇Ge〇2 〇〇1 1 Bi2〇3 1 1 1 1 Raw material powder blending amount/mol% B12O3 Ge〇2 Bii2Ge〇2〇16.7 33.3 1 16.7 83.3 66.7 0 83.3 1 1 1 Bi/(Bi + Ge) 0.67 0.80 0.67 0.67 Dry composition/mol% B12O3 Ge〇2 〇33.3 66.7 I Example 11 1 Example 2 1 Comparative Example 1 Comparative Example 2 201142058 (Example 2) A powder having a purity of 3 Ν (99·9%) of dioxon and cerium oxide was used as a starting point Raw materials, and Ge 〇 2 powder having an average particle diameter of 〖2 # m and Βίκό ε Ο π powder having an average particle size of 20 # m are prepared in advance, and the ratio of the atomic ratio of Bi to ~ is 0.80, respectively. 2 powder 66 7 m〇1% and BiuGeOuS 33.3 mol%, and then mixed, and the mixed powder was filled in a carbon mold, and hot pressed at a temperature of 700 t: and a pressure of 25 〇 kg/cm 2 . In the case of returning to the ear, the addition of Dan is in the form of 〇2 powder, Bl|2Ge〇2G #, and the added ratio of these additions is

The blend ratio of Ge〇233.3 mol% and Bi2〇366.7 mol% was adjusted. ° ° The sintered body after hot pressing is finished to make a handle. The relative density of the dry is 95.9% (7 58 g/cm3 at 1% density). The X-ray diffraction measurement of the sintered body confirmed the three-phase structure of Bi|2Ge〇2 and Ge〇2. The results are shown in Table 1. 20 Next, apply 200t for 30 minutes and heat for 30 minutes. In the absence of the bending test of JIS Standard 1601, the thermal shock = the ratio of the curvature f (the rate of decrease in strength) was measured. Difficult deviations occur due to differences in measurement sites, but none of them are as low as 5〇%. Secondly, using this dry material, the (4) H target is not cracked or cracked at a power of 2 kW, and the generation of particles is small. ,,,,,. As a result, the embodiment of the present invention has the following excellent targets: no cracking or seaming can be produced, and the production efficiency can be improved. 2: Producing a high-quality film of 201142058 quality can be obtained without generating recording bits. Error light recording media. (Comparative Example 1) A powder having a purity of 3N (99.9%) of antimony trioxide and cerium oxide was used as a starting material, and the average particle diameter was 5 such that the atomic ratio of Bi to Ge was 〇67. After the GeCh powder of 50 m_〇m〇l% and the Bi2〇3 powder having an average particle diameter of 20 // m 50.0 mol%, the mixture was mixed, and the mixed powder was filled in a carbon mold at a temperature of 73 ( The hot melt was performed under the conditions of rc and a pressure of 25 〇kg/cm2. The sintered body after the hot pressing was finished to obtain a target, and the relative density of the target was 103% (7.44 g/cm3 at 100% density). The X-ray diffraction of the sintered body was measured and confirmed, and the crystal phase of the target was confirmed to be

2-phase structure of Bii2Ge02〇 and Bi4Ge3012. Next, a thermal shock of 20 CTC and heating for 30 minutes was applied to the target. Then, the average bending strength test of JIS1601 was carried out, and the measurement results of the average bending strength ratio (reduction rate of strength) before and after the thermal shock were similarly shown in Table 1. 'The result' The average bending strength reduction rate was 82%. Using this handle, sputtering was performed at a power of 2 kW. As a result, cracks are generated in the target during sputtering. Moreover, the generation of particles is significantly increased as compared with the examples. It is considered that the cause is a crack in the target in sputtering. (Comparative Example 2) A powder of trioxide and cerium oxide having a purity of 3N (99% to 9%) is used as a starting material, and an average particle diameter of Ge 〇 2 is prepared in advance. Powder and flat 201142058 Bi丨2Ge02〇 powder with a particle size of 20 μm, respectively, after blending the Ge02 powder 83.3mol% 'Bi12GeO20 powder 16.7mol% with the atomic ratio of Bi to Ge to be 0.66, The force σ was mixed, and the mixed powder was filled in a carbon mold, and hot pressed at a temperature of 700 ° C and a pressure of 250 kg/cm 2 . Furthermore, in the present embodiment, GeCh powder and Bi^GeOu powder are added in such a manner as to achieve the above molar ratio, and the combined ratios of the additions are 0.0m〇l% and Bi20350.0mol% of GeO25. Adjustment by blending method 0 The sintered body after hot pressing is finished to form a target. The relative density of the target was 103% (7.58 g/cm3 at 10% density). From the X-ray diffraction measurement of the sintered body, it was confirmed that the Ge 〇 total amount reacted and was a two-phase structure of Bil2Ge〇2Q and Bi4Ge3〇i2. For a long time, it applied a thermal shock of 200 ° C for 30 minutes to dry. Then, the average bending strength test of JIS 1 60 1 was carried out. Similarly, the measurement result of the average bending strength ratio (reduction rate of the strength) after the heat balance was shown in Table 1 °, and the result of the decrease in the average bending strength was 80%. This target was used to perform sputtering at a power of 2 kW. As a result, cracks are generated in the target during sputtering. Moreover, the generation of particles is significantly increased as compared with the examples. The cause is considered to be a crack in the target in the sputtering. INDUSTRIAL APPLICABILITY The B1-Ge-bismuth sintered body sputtering target and the method for preparing the target according to the present invention have the following excellent effects: no cracking of the target occurs during sputtering 15 201142058 slit, particle The production is small, and a high-quality film can be stably produced, and an optical recording medium that does not cause a recording bit error can be obtained. It is possible to provide a production efficiency capable of improving the film formation of an optical recording medium, and is suitable for manufacturing an optical recording medium. [Simple diagram description] None [Main component symbol description] None 16

Claims (1)

201142058 VII. Patent application scope: 1. A Bi-Ge-0 sintered body sputtering target consisting of bismuth (Bi), germanium (Ge) and oxygen (〇), characterized by: the number of atoms of Bi and Ge The ratio is 0.57 &lt; (Bl / (Bi + (} e)) &lt; ()%, containing 3 phases of Bi12GeO20, Bi4Ge3〇l2, Ge〇2 as a crystal phase. 2. The sintered body of claim 1 In the sputtering target, when the thermal shock of heating for 200t and 30 minutes is applied to the target, the average bending strength reduction rate before and after the thermal shock is 50% or less. 3. Optical recording medium: the patent application scope is used. Or a target of two targets is formed by sputtering. 4. A method for producing a Bi-Ge-lanthanum sintered body by dry plating, characterized in that: 0.03 to 89 mol% of Ge02 powder, and 11 to 99.97 mol of Bi丨2Ge02 powder. /〇 as a starting material, after mixing the raw materials in such a manner that the atomic ratio of Βι to Ge is 〇57 &lt;(Bi/(Bi + Ge))&lt;0.92, at 6〇〇~84〇χ: A sintered body containing a crystal phase of three phases of Bii2GeO20, Bi4Ge3012, and Ge02 is prepared by applying a hot press at a pressure of 150 to 400 kg/cm2. A method for producing a Bi-Ge-based sintered body sputtered leather, wherein the Ge〇2 powder 14 3ηιο1〇/〇 is mixed with the Bi203 powder at 85.7 m〇%, and then subjected to a solid phase reaction. Bii2Ge〇2() powder. 6. Bi-Ge- 0 sintered body according to the fourth or fifth aspect of the patent application (manufacturing method of recording '), wherein the average crystal grain size is 1 〇~5 〇# Sintering raw material powder of cerium oxide is sintered.