Sputtering target and manufacturing method therefor
11718907 · 2023-08-08
Assignee
Inventors
Cpc classification
H01J37/3435
ELECTRICITY
C22C9/06
CHEMISTRY; METALLURGY
C23C14/3414
CHEMISTRY; METALLURGY
International classification
C22C9/06
CHEMISTRY; METALLURGY
Abstract
A sputtering target according to one embodiment is an integrated sputtering target comprising a target portion and a backing plate portion, both of them being made of copper and unavoidable impurities, wherein a Vickers hardness Hv is 90 or more, and wherein a flat ratio of crystal grains in a cross section orthogonal to a sputtering surface is 0.35 or more and 0.65 or less.
Claims
1. An integrated sputtering target comprising a target portion forming a front surface layer of the sputtering target and a backing plate portion, which is integral with the target portion, forming a back surface layer of the sputtering target, both of the target portion and the backing plate portion being made of copper and unavoidable impurities, wherein an entirety of the integrated sputtering target has a Vickers hardness Hv of 90 or more, and wherein a flat ratio of crystal grains in a cross section orthogonal to a sputtering surface to be used for sputtering is 0.35 or more and 0.65 or less.
2. The sputtering target according to claim 1, wherein the target portion and the backing plate portion further contain one or more elements selected from the group consisting of Fe, Cr, Ni, Si, Ag, S, and P in a total nonzero amount up to 0.01% by mass.
3. A method for manufacturing the integrated sputtering target according to claim 1, the method comprising: melting a raw material to cast an ingot comprising copper and unavoidable impurities; and subjecting the ingot to hot forging, first cold rolling or first cold forging, a heat treatment, and second cold rolling or second cold forging in this order, wherein the second cold rolling or the second cold forging is carried out at a change rate of from 20% to 40%, and wherein in the second cold rolling or the second cold forging, crystal grains are crushed in a thickness direction to change a flat ratio of the crystal grains in a cross section orthogonal to a sputtering surface to be used for sputtering.
4. The method according to claim 3, wherein the heat treatment is carried out at a temperature of from 200° C. to 500° C. for 0.5 hours to 3 hours.
5. The method according to claim 3, wherein the first cold rolling or the first cold forging is carried out at a change rate of 70% or more.
6. The method according to claim 3, wherein the hot forging is carried out at a temperature of from 300° C. to 900° C.
7. The method according to claim 3, wherein the ingot further contains one or more elements selected from the group consisting of Fe, Cr, Ni, Si, Ag, S, and P in a total amount of 0.01% mass or less.
8. The sputtering target according to claim 1, wherein the sputtering target has an average crystal grain size of 10 μm or more and 60 μm or less.
Description
BRIEF DESCRIPTION OF DRAWINGS
(1) The patent or application file contains at least one drawing executed in color. Copies of this patent or patent application publication with color drawings will be provided by the Office upon request and payment of the necessary fee.
(2)
DESCRIPTION OF THE PREFERRED EMBODIMENTS
(3) Hereinafter, embodiments of the invention disclosed in the specification will be described in detail.
(4) <Sputtering Target and Manufacturing Method According to First Embodiment>
(5) A sputtering target according to this embodiment is of integrated type including: a disk-shaped target portion; and a backing plate portion which has substantially the same shape as the target portion and is integral with the target portion, in which both of the target portion and the backing plate portion are made of equivalent copper and unavoidable impurities, and in which a Vickers hardness Hv is 90 or more, and a flat ratio of crystal grains in a cross section orthogonal to a sputtering surface is 0.35 or more and 0.65 or less. In the present embodiment, the sputtering target generally has a plate shape such as a disk shape, but may include other shapes. Whether or not the sputtering target is of integral type can be determined by confirming whether or not materials of a front surface and a back surface of the sputtering target are the same as each other. Since the sputtering target is made of cupper, the determination can be made by measuring conductivity.
(6) (Composition)
(7) In the sputtering target according to the present embodiment, both of the target portion and the backing plate portion contain copper as a main component, and may further contain at least other elements as long as the Vickers hardness Hv as described below will be maintained to be 90 or more. The copper content in the target portion and the backing plate portion is preferably 99.99% by mass or more, and more preferably 99.9999% by mass or more. If the copper content is too low, there is a concern that serious defects may occur when used in semiconductor products.
(8) Both of the target portion and the backing plate portion may be comprised only of copper, but they may contain, as the impurities as described above, one or more element selected from the group consisting of Fe, Cr, Ni, Si, Ag, S and P, for example in a total amount of 0.01% by mass or less, and preferably 0.005% by mass or less. If the total content of the above elements is more than 0.01% by mass, serious defects may occur when used in semiconductor products.
(9) However, the elements are not limited to those listed herein, and other elements can be contained as long as the Vickers hardness Hv of 90 or more can be ensured.
(10) (Vickers Hardness)
(11) The sputtering target according to the present embodiment has a Vickers hardness Hv of 90 or more. This can allow suppression of warpage during sputtering, even if the sputtering target provided with the backing plate portion which mainly consists of copper as in the target portion, and even if it is such a sputtering target having a diameter of more than 400 mm for example. As a result, effective sputtering can be carried out until the latter half of the life of the sputtering target. From this viewpoint, the Vickers hardness Hv of the sputtering target is 90 or more, and preferably 97 or more.
(12) On the other hand, if the hardness is too high, there is a concern that recrystallization may occur during sputtering due to heat caused by sputtering, resulting in softening. Therefore, the Vickers hardness Hv may be, for example, 125 or less, and preferably 118 or less.
(13) The Vickers hardness Hv is measured in accordance with JIS Z2244 (2009). In the sputtering target in which the target portion and the backing plate portion are integrated, the Vickers hardness Hv of the target portion and the backing plate portion is substantially the same.
(14) Such Vickers hardness Hv can be obtained, for example, by production according to the manufacturing method as described later.
(15) (Average Crystal Grain Size)
(16) In the sputtering target according to the embodiment, an average crystal grain size is preferably 10 μm or more and 60 μm or less. If the average crystal grain size is less than 10 μm, an erosion rate during sputtering may be decreased, and if it is more than 60 μm, film uniformity during sputtering may be deteriorated. Therefore, the average crystal grain size is more preferably 20 μm or more and 50 μm or less, and still more preferably 25 μm or more and 45 μm or less.
(17) The average crystal grain size is measured by observation with an optical microscope. More particularly, as shown in
(18) (Flat Ratio of Crystal Grains)
(19) In the sputtering target according to the embodiment, a flat ratio of crystal grains present in a cross section along a plane orthogonal to the sputtering surface is 0.35 or more and 0.65 or less.
(20) The flat ratio is determined using an optical microscope as follows: total four arbitrary straight lines, two straight lines in each of a target thickness direction and a direction perpendicular to the target thickness direction of the crystal grains observed in the cross section, are drawn (see “Cross-sectional Texture” in
(21) If the above flat ratio is less than 0.35, the strength would be insufficient because processing deformation of a recrystallized structure is not sufficient. On the other hand, if it is more than 0.65, the erosion rate may decrease because the grain size in the thickness direction is too fine. Further, when the flat ratio is more than 0.65 in pure copper, there is a concern that a recrystallization temperature is decreased due to processing deformation, thereby resulting in softening due to the heat caused by sputtering during sputtering.
(22) Therefore, in the sputtering target according to the embodiment, the flat ratio of crystal grains present in the cross section along the plane orthogonal to the sputtering surface is 0.35 or more and 0.65 or less, and preferably 0.40 or more and 0.60 or less, and more preferably 0.45 or more and 0.55 or less.
(23) The flat ratio of crystal grains in the cross section can be obtained, for example, by production according to the manufacturing method as described later.
(24) (Manufacturing Method)
(25) The sputtering target according to the embodiment can be manufactured, for example, as follows.
(26) First, high purity copper having a purity of 4N or 6N is melted at a temperature of from 1080° C. to 1280° C. for 0.5 hours to 6 hours, and cooled and harden in a predetermined mold, thereby casting an ingot comprised of copper and unavoidable impurities as a material for the sputtering target in which the target portion and the backing plate are integrated.
(27) The ingot is then subjected to hot forging, first cold rolling or first cold forging, a heat treatment, and second cold rolling or second cold forging.
(28) Here, the hot forging is preferably carried out at a temperature of from 300° C. to 900° C. This is because if the temperature during forging is less than 300° C., there is a risk of cracking in the ingot during forging, whereas if it is more than 900° C., copper is abnormally softened, which is dangerous, and abnormal grain growth during forging may take place due to the elevated temperature.
(29) Here, the first cold rolling and the first cold forging are preferably carried out at a change rate of 70% or more, in terms of sufficiently destroying the cast structure. As used herein, the change rate R (%) means a ratio of dimensional changes in the thickness direction, represented by the equation: R=(T1−T2)/T1×100, in which T1 represents a thickness of a target material before rolling or forging, and T2 represents a thickness of a target material after rolling or forging. More particularly, in the case of rolling, the above change rate corresponds to a so-called rolling reduction, which is also calculated by the same equation. The same is true for change rates of the second cold rolling and the second cold forging which will be described later. When calculating the change rate, the thickness of the target material is measured by firstly confirming a sufficiently flat surface of the target material having a disk shape or the like by a flat rod as a base, and then measuring four thicknesses in a circumferential direction at a position of 50 mm in a central direction from a periphery of the target material.
(30) The temperature during the first cold rolling or the first cold forging is, for example, about 10° C. to 100° C.
(31) The heat treatment after the first cold rolling or the first cold forging is preferably carried out at a temperature of from 200° C. to 500° C. for 0.5 hours to 3 hours. This is because recrystallization would not be sufficiently promoted at a lower temperature of less than 200° C. and strain partially would remain, while grains would become abnormally coarse at a higher temperature of more than 500° C. Further, if the heat treatment is carried out for a shorter period of time, recrystallization cannot be sufficiently promoted and strain may partially remain, while if it is carried out for a longer period of time, the grains may become abnormally coarse.
(32) After the heat treatment, the second cold rolling or the second cold forging is further carried out. The change rate of the second cold rolling or the second cold forging is from 20% to 40%. This can allow introduction of strain into the target material to increase effectively the hardness of the manufactured sputtering target. Further, as a result of crystal grains being crushed in the thickness direction by carrying out the second cold rolling or the second cold forging, the flat ratio of the crystal grains in the above cross section of the sputtering target will be 0.35 or more and 0.65 or less.
(33) If the change rate of the second cold rolling or the second cold forging is less than 20%, the hardness of the sputtering target cannot be sufficiently increased, and the risk of warpage during sputtering cannot be eliminated. On the other hand, if the change rate of the second cold rolling or the second cold forging is larger than 40%, a decrease in the recrystallization temperature due to the introduction of strain becomes remarkable and the sputtering target is softened due to the heat during sputtering, so that in this case, there is also a concern that the sputtering target may be warped.
(34) From such a point of view, the change rate of the second cold rolling or the second cold forging is preferably from 20% to 40%, and more preferably from 25% to 35%.
(35) The temperature during the second cold rolling or second cold forging is, for example, from about 10° C. to 100° C.
(36) In the second cold rolling or the second cold forging, water cooling is preferably carried out every one pass of the rolling or forging or every one rolling or one forging, in order to prevent relaxation of the introduced strain due to the working heat of the rolling or forging.
(37) Subsequently, finishing processing such as cutting can be performed as needed to manufacture a sputtering target.
(38) <Sputtering Target and Manufacturing Method According to Second Embodiment>
(39) A sputtering target according to this embodiment is of integrated type including: a disk-shaped target portion; and a backing plate portion which has substantially the same shape as the target portion and is integral with the target portion, in which both of the target portion and the backing plate portion are made of an equivalent copper alloy, and in which a Vickers hardness Hv is 90 or more, and a flat ratio of crystal grains in a cross section orthogonal to a sputtering surface is 0.35 or more and 0.85 or less. In the present embodiment, the sputtering target generally has a plate shape such as a disk shape, but may include other shapes. Whether or not the sputtering target is of integrated type can be determined by confirming whether or not materials of a front surface and a back surface of the sputtering target are the same as each other. Since the sputtering target is made of cupper, the determination can be made by measuring conductivity.
(40) (Composition)
(41) In the sputtering target according to the present embodiment, both of the target portion and the backing plate portion contain copper as a main component, and also contain at least one element selected from aluminum, manganese, nickel and cobalt as a sub component in an amount of from 0.1% by mass to 8% by mass, and it may further contain other elements as long as the Vickers hardness Hv as described below will be maintained to be 90 or more. Both of the target portion and the backing plate portion are made of a copper alloy having the same composition.
(42) The total content of the sub components of the copper alloy forming the target portion and the backing plate portion is from 0.1% by mass to 8% by mass, when the sub components are a plurality of types of elements. If the content of the sub component is too high, conductivity is significantly reduced so that it is difficult to use the target as a wiring material. On the other hand, if the content of the sub component is too low, it may be difficult to produce a target in which the alloy component is uniformly dispersed. From this viewpoint, the content of the sub component is from 0.1% by mass to 8% by mass, and preferably from 0.1% by mass to 6% by mass, and more preferably from 0.2% by mass to 6% by mass. More suitably, the content of the sub component is 0.1% by mass or more as a lower limit, and preferably 0.2% by mass or more, and 8% by mass or less as an upper limit, and preferably 6% or less, and more preferably 5% by mass or less, and even more particularly 4% by mass or less. Examples of a copper alloy sputtering target containing two or more types of sub components include those containing manganese and aluminum.
(43) Both of the target portion and the backing plate portion may further contain, as impurities, one or more selected from the group consisting of Fe, Cr, Si, Ag, S and P, for example in a total amount of 0.01% by mass or less, and preferably 0.005% by mass or less. If the total content of the above elements is more than 0.01% by mass, serious defects may take place when used in semiconductor products.
(44) However, the elements are not limited to those listed herein, and other elements can be contained as long as the Vickers hardness Hv of 90 or more can be ensured.
(45) (Vickers Hardness)
(46) The sputtering target according to the present embodiment has a Vickers hardness Hv of 90 or more. This can allow suppression of warpage during sputtering, even if the sputtering target provided with the backing plate portion which mainly consists of the copper alloy as in the target portion, and even if it is such a sputtering target having a diameter of more than 400 mm for example. As a result, effective sputtering can be carried out until the latter half of the life of the sputtering target. From this viewpoint, the Vickers hardness Hv of the sputtering target is 90 or more, and preferably 97 or more.
(47) In addition, the generation of warpage in the sputtering target causes problems that uniformity of a thin film to be formed decreases and plasma falls. However, in this embodiment, since the sputtering target has the Vickers hardness Hv as described above, such problems are not caused.
(48) The Vickers hardness Hv is measured in accordance with JIS Z2244 (2009). In the sputtering target in which the target portion and the backing plate portion are integrated, the Vickers hardness Hv of the target portion and the backing plate portion is substantially the same.
(49) Such Vickers hardness Hv can be obtained, for example, by production according to the manufacturing method as described later.
(50) (Average Crystal Grain Size)
(51) In the sputtering target according to the embodiment, the average crystal grain size is preferably 5 μm or more and 50 μm or less. If the average crystal grain size is less than 5 μm, an erosion rate during sputtering may be decreased, and if it is more than 50 μm, film uniformity during sputtering may be deteriorated. Therefore, the average crystal grain size is more preferably 20 μm or more and 50 μm or less, and still more preferably 25 μm or more and 45 μm or less.
(52) The average crystal grain size is measured by observation with an optical microscope. More particularly, as shown in
(53) (Flat Ratio of Crystal Grains)
(54) In the sputtering target according to the embodiment, a flat ratio of crystal grains present in a cross section along a plane orthogonal to the sputtering surface is 0.35 or more and 0.85 or less.
(55) The flat ratio is determined using an optical microscope as follows: total four arbitrary straight lines, two straight lines in each of a target thickness direction and a direction perpendicular to a target thickness direction of the crystal grains observed in the cross section, are drawn (see “Cross-sectional Texture” in
(56) If the above flat ratio is less than 0.35, the strength would be insufficient because processing deformation of a recrystallized structure is not sufficient. On the other hand, if it is more than 0.85, a voltage may be too high due to large internal stress in the sputtering target when sputtering is performed, so that the life of the sputtering target may be shortened.
(57) Therefore, in the sputtering target according to the embodiment, the flat ratio of crystal grains present in a cross section along a plane orthogonal to the sputtering surface is 0.35 or more and 0.85 or less, and preferably 0.40 or more and 0.60 or less, more preferably 0.45 or more and 0.55 or less.
(58) The flat ratio of crystal grains of the cross section can be obtained, for example, by production according to the manufacturing method as described later.
(59) (Manufacturing Method)
(60) The sputtering target according to the embodiment can be manufactured, for example, as follows.
(61) First, at least one element selected from aluminum, manganese, nickel and cobalt is added to high purity copper having a purity of 4N or 6N so as to have the predetermined composition as described above, and melted at a temperature of from 1080° C. to 1280° C. for 0.5 hours to 6 hours, and cooled and harden in a predetermined mold, thereby casting an ingot comprising the element, copper and unavoidable impurities as a material for the sputtering target in which the target portion and the backing plate are integrated.
(62) The ingot is then subjected to hot forging, first cold rolling or first cold forging, a heat treatment, and second cold rolling or second cold forging.
(63) Here, the hot forging is preferably carried out at a temperature of from 300° C. to 900° C. This is because if the temperature during forging is less than 300° C., there is a risk of cracking in the ingot during forging, whereas if it is more than 900° C., copper is abnormally softened, which is dangerous, and abnormal grain growth during forging may take place due to the elevated temperature.
(64) Here, the first cold rolling and the first cold forging are preferably carried out at a change rate of 70% or more, in terms of sufficiently destroying the cast structure. As used herein, the change rate R (%) means a ratio of dimensional changes in the thickness direction, represented by the equation: R=(T1−T2)/T1×100, in which T1 represents a thickness of a target material before rolling or forging, and T2 represents a thickness of a target material after rolling or forging. More particularly, in the case of rolling, the above change rate corresponds to a so-called rolling reduction, which is also calculated by the same equation. The same is true for change rates of the second cold rolling and the second cold forging which will be described later. When calculating the change rate, the thickness of the target material is measured by firstly confirming a sufficiently flat surface of the target material having a disk shape or the like by a flat rod as a base, and then measuring four thicknesses in a circumferential direction at a position of 50 mm in a central direction from a periphery of the target material.
(65) The temperature during the first cold rolling or the first cold forging is, for example, about 10° C. to 100° C.
(66) The heat treatment after the first cold rolling or the first cold forging is preferably carried out at a temperature of from 200° C. to 500° C. for 0.5 hours to 3 hours. This is because recrystallization cannot be sufficiently promoted at a lower temperature of less than 200° C. and strain may partially remain, while grains may become abnormally coarse at a higher temperature of more than 500° C. Further, if the heat treatment is carried out for a shorter period of time, recrystallization cannot be sufficiently promoted and strain may partially remain, while if it is carried out for a longer period of time, the grains may become abnormally coarse.
(67) After the heat treatment, the second cold rolling or the second cold forging is further carried out. The change rate of the second cold rolling or the second cold forging is from 20% to 60%. This can allow introduction of strain into the target material to increase effectively the hardness of the manufactured sputtering target. Further, as a result of crystal grains being crushed in the thickness direction by carrying out the second cold rolling or the second cold forging, the flat ratio of the crystal grains in the above cross section of the sputtering target will be 0.35 or more and 0.85 or less. Furthermore, by controlling an amount of strain introduced into the target material in the second cold rolling or the second cold forging, an increase in sputtering voltage due to the internal stress during sputtering can be suppressed, so that the sputtering target can be used for a longer period of time.
(68) If the change rate of the second cold rolling or the second cold forging is less than 20%, the hardness of the sputtering target cannot be sufficiently increased, and the risk of warpage during sputtering cannot be eliminated. On the other hand, if the change rate of the second cold rolling or the second cold forging is larger than 60%, the voltage is too high due to large internal stress in the sputtering target when sputtering is performed, so that the life of the sputtering target is shortened.
(69) From such a point of view, the change rate of the second cold rolling or the second cold forging is preferably from 20% to 40%, in particular from 25% to 35%.
(70) The temperature during the second cold rolling or second cold forging is, for example, from about 10° C. to 100° C.
(71) In the second cold rolling or the second cold forging, water cooling is preferably carried out every one pass of the rolling or forging or every one rolling or one forging, in order to prevent relaxation of the introduced strain due to the processing heat of the rolling or forging.
(72) Subsequently, finishing processing such as cutting can be performed as needed to manufacture a sputtering target.
EXAMPLES
(73) Next, the sputtering target was experimentally manufactured and its effects were confirmed as described below. However, the description herein is merely for the purpose of illustration and is not intended to be limited thereto.
Test Example 1
(74) High purity copper having a purity of 6N was melted in a crucible at a temperature of 1100° C. for 1 hour, and the resulting molten metal was then cast in a mold to form an ingot having a diameter of 220 mm and a thickness of 210 mm. The ingot was then subjected to hot forging at a temperature of 500° C. to have dimensions of a diameter of 160 mm and a thickness of 250 mm, and then subjected to first cold forging or first cold rolling to provide a target material having a diameter of 470 mm and a thickness of 45 mm. The target material was then subjected to a heat treatment at 300° C. for 1 hour and cooled, and then subjected to second cold rolling or second cold forging at each change rate as shown in Table 1. Further, the target material was subjected to cutting processing to produce a sputtering target in which a target portion and a backing plate portion were integrated.
(75) In Examples 1-1 to 1-3 and Comparative Examples 1-1 and 1-2, sputtering targets were produced under the same conditions, with the exception that the change rate of the second cold rolling or the second cold forging after the heat treatment varied as shown in Table 1.
(76) For each of Examples 1-1 to 1-3 and Comparative Examples 1-1 and 1-2, the Vickers hardness of each sample of the produced sputtering targets, and the Vickers hardness after further heating the sample at 140° C. for 1 hour, the average crystal grain size, and the flat ratio of crystal grains in a cross section were determined.
(77) Further, sputtering was carried out to 2500 kWhr according to a recommended recipe using the sputtering targets of Examples 1-1 to 1-3 and Comparative examples 1-1 and 1-2, and the warpage of each target at the end of sputtering was measured. Here, the warpage of each target was determined by measuring the back surface of the target by means of a three-dimensional measuring device.
(78) These results are also shown in Table 1.
(79) TABLE-US-00001 TABLE 1 Flat Rate Change Rate Sample After Heating Average of Grains in of Second Vickers Vickers Crystal a Cross Section Warpage after Rolling Hardness Hardness Grain Size (1 - Short Side/ Sputtering Material Impurities (%) (Hv) (Hv) (μm) Long Side) (mm) Example 1-1 Cu — 20 93 80 45 0.36 0.9 Example 1-2 Cu — 30 100 70 40 0.51 0.6 Example 1-3 Cu — 40 104 70 35 0.64 0.5 Comparative Cu — 10 91 83 40 0.19 2.1 Example 1-1 Comparative Cu — 50 106 55 35 0.75 1.7 Example 1-2
(80) The results shown in Table 1 demonstrate that Examples 1-1 to 1-3 where the second cold rolling or the second cold forging after the heat treatment was carried out at a change rate in the range of from 20% to 40% had higher measured values for the Vickers hardness, and as a result, the generation of warpage during sputtering was effectively suppressed.
(81) On the other hand, Comparative Example 1-1 where the change rate of the second cold rolling or the second cold forging was less than 20% had lower measured values for the Vickers hardness, and larger warpage occurred during sputtering accordingly.
(82) In Comparative Example 1-2 where the change rate of the second cold rolling or the second cold forging was higher than 40%, the measured values for the Vickers hardness were increased, but relatively large warpage occurred during sputtering. Considering that the Vickers hardness is reduced after heating in Comparative Example 1-2, it is believed that in Comparative Example 1-2, the recrystallization temperature decreases as strain is introduced, and when large strain is introduced at the change rate of about 50%, the softening due to heat during sputtering occurs, thereby causing the large warpage.
Test Example 2
(83) High purity copper having a purity of 6N and aluminum or manganese were placed in a crucible so as to have a predetermined composition, and melted in the crucible at a temperature of 1100° C. for 1 hour, and the resulting molten metal was then cast in a mold to form an ingot having a diameter of 220 mm and a thickness of 210 mm. The ingot was then subjected to hot forging at a temperature of 500° C. to have dimensions of a diameter of 160 mm and a thickness of 250 mm, and then subjected to first cold forging or first cold rolling to provide a target material having a diameter of 470 mm and a thickness of 45 mm. The target material was subjected to a heat treatment at 300° C. for 1 hour and cooled, and then subjected to second cold rolling or second cold forging at each change rate as shown in Table 2. Further, the target material was subjected to cutting processing to produce a sputtering target in which a target portion and a backing plate portion were integrated.
(84) In Examples 2-1 to 2-9 and Comparative Examples 2-1 to 2-6, sputtering targets were produced under the same conditions, with the exception that the change rate of the second cold rolling or the second cold forging after the heat treatment varied as shown in Table 2.
(85) For each of Examples 2-1 to 2-9 and Comparative Examples 2-1 to 2-6, the Vickers hardness, the average crystal grain size, and the flat ratio of crystal grains in a cross section of each of produced sputtering targets were determined.
(86) Further, sputtering was carried out to 3200 kWhr according to a recommended recipe using the sputtering targets of Examples 2-1 to 2-9 and Comparative examples 2-1 to 2-6, and a target life and warpage of each target at the end of sputtering were measured.
(87) It should be noted that the target life was obtained as power consumption (power×time) during sputtering. As the power consumption is higher, the sputtering can be carried out at higher power for a longer period of time, which means that the life of the sputtering target is longer. Further, the warpage of each target was determined by measuring the back surface of the target by means of a three-dimensional measuring device.
(88) These results are also shown in Table 2. It should be noted that since the target life greatly depends on the sputtering conditions, Table 2 also shows indices normalized on the basis of Example 2-1.
(89) TABLE-US-00002 TABLE 2 Flat Rate Change Rate Average of Grains in of Second Vickers Crystal a Cross Section Warpage after Composition Rolling Hardness Grain Size (1 - Short Side/ Target Life Sputtering Material (% by mass) (%) (Hv) (μm) Long Side) (Normalized) (mm) Example 2-1 CuAl 0.1 20 99 30 0.36 100% 0.8 Example 2-2 CuAl 0.1 30 105 35 0.51 100% 0.4 Example 2-3 CuAl 0.1 60 113 25 0.84 100% 0.4 Example 2-4 CuMn 0.5 20 100 35 0.36 100% 0.9 Example 2-5 CuMn 0.5 30 109 30 0.51 100% 0.3 Example 2-6 CuMn 0.5 60 116 20 0.84 100% 0.7 Example 2-7 CuMn 4.0 20 121 15 0.36 100% 0.3 Example 2-8 CuMn 4.0 30 130 10 0.51 100% 0.4 Example 2-9 CuMn 4.0 60 138 10 0.84 100% 0.3 Comparative CuAl 0.1 10 80 30 0.19 1% 2.0 Example 2-1 Comparative CuAl 0.1 90 128 <5 0.99 79% 1.1 Example 2-2 Comparative CuMn 0.5 10 84 30 0.19 1% 2.2 Example 2-3 Comparative CuMn 0.5 90 131 <5 0.99 84% 0.9 Example 2-4 Comparative CuMn 4.0 10 88 15 0.19 1% 2.1 Example 2-5 Comparative CuMn 4.0 90 144 <5 0.99 90% 0.5 Example 2-6
(90) The results shown in Table 2 demonstrate that Examples 2-1 to 2-9 where the second cold rolling or the second cold forging after the heat treatment was carried out at a change rate in the range of from 20% to 60% had higher measured values for the Vickers hardness, and as a result, the generation of warpage during sputtering was effectively suppressed.
(91) On the other hand, Comparative Examples 2-1, 2-3 and 2-5 where each change rate of the second cold rolling or the second cold forging was less than 20% had lower measured values for the Vickers hardness, and larger warpage occurred during sputtering accordingly.
(92) Comparative Examples 2-2, 2-4 and 2-6 where each change rate of the second cold rolling or the second cold forging was higher than 60% had increased measured values for the Vickers hardness, but they resulted in increased flat ratios of crystal grains in a cross section. This resulted in an increased voltage during sputtering due to an increase in internal stress, thereby reaching the limit of the apparatus in the latter half of the life.
(93) According to Examples as described above, it was found that an integrated sputtering target that can be manufactured at low cost can increase hardness of the target to suppress warpage during sputtering effectively.