WO2013133353A1 - Cible de pulvérisation - Google Patents

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Publication number
WO2013133353A1
WO2013133353A1 PCT/JP2013/056231 JP2013056231W WO2013133353A1 WO 2013133353 A1 WO2013133353 A1 WO 2013133353A1 JP 2013056231 W JP2013056231 W JP 2013056231W WO 2013133353 A1 WO2013133353 A1 WO 2013133353A1
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Prior art keywords
sputtering
target
copper
ppm
sputtering target
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PCT/JP2013/056231
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English (en)
Japanese (ja)
Inventor
栄徳 尹
安藤　俊之
上田　健一郎
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古河電気工業株式会社
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Priority claimed from JP2012053267A external-priority patent/JP5950632B2/ja
Priority claimed from JP2012053266A external-priority patent/JP6182296B2/ja
Application filed by 古河電気工業株式会社 filed Critical 古河電気工業株式会社
Priority to KR1020147018216A priority Critical patent/KR20140138111A/ko
Priority to CN201380004880.3A priority patent/CN104080943B/zh
Publication of WO2013133353A1 publication Critical patent/WO2013133353A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
    • C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon

Definitions

  • the present invention includes, for example, a metal thin film constituting a flat panel display element represented by a liquid crystal display, a light shielding film constituting a mask for manufacturing a semiconductor element, a metal wiring constituting a semiconductor element such as LSI, and a magnetic recording medium And a sputtering target made of high purity copper for forming a copper thin film etc.
  • the sputtering method is used as a method for forming the copper thin film etc. which were mentioned above in a to-be-sputtered thing.
  • the above sputtering target (hereinafter, also referred to as "target") is set in a form facing the sputtering target such as a substrate, and a gas such as Ar is flowed under vacuum conditions.
  • the film forming method is to form a thin film having the same composition as the target on the sputtering target by causing the ionized Ar to collide with the target by causing discharge by applying a predetermined voltage between the sputtering surface and the sputtering target. .
  • Such a sputtering method is applied to various fields such as a semiconductor element, a magnetic recording medium, a mask for manufacturing a semiconductor element, a component such as a liquid crystal display, and the like through a process corresponding to each purpose.
  • the substance sputtered from the target originally adheres to a sputtering target such as a substrate facing the sputtering target, the substance is not necessarily sputtered vertically and flies in various directions. .
  • Such incident materials are called particles, and when they are clustered and directly attached to the substrate, or attached to equipment in the sputtering apparatus other than the substrate, they sometimes come off and float, and they are re-deposited on the substrate. May adhere.
  • Abnormal film formation problems such as generation of coarse clusters are considered to occur due to surface conditions such as the orientation of the target itself and surface roughness, in addition to sputtering conditions in the sputtering process.
  • the sputtering target is adjusted to a predetermined surface roughness that can reduce generation of nodules and particles, for example, by performing machining, polishing, chemical etching, etc. on the sputtering target to be used as a sputtering target.
  • a sputtering target and a method of manufacturing the same are disclosed.
  • Patent Document 1 in order to improve the surface state of the target itself, those focusing on the surface roughness of the target itself and the orientation of the structure have been proposed.
  • Technology has been proposed to reduce the content of heavy metals such as iron and nickel in order to prevent oxidation, and the current measures are sufficient to prevent film formation abnormalities that occur with cracking of the target surface. There was a problem that it could not prevent.
  • this invention prevents generation
  • the present invention is a sputtering target mainly composed of copper having a purity of 99.9% by mass or more, and contains 10 ppm or less of sulfur (S) and 2 ppm or less of lead (Pb). .
  • ppm means mass ppm.
  • the purity of the copper is 99.96% by mass or more.
  • the target surface and a target having a crack ( ⁇ ) with a width greater than or equal to a predetermined size can be greatly reduced on the target surface and in the inside, thereby preventing generation of abnormal discharge (arcing) during sputtering processing.
  • the purity of copper is preferably 99.96% by mass or more, and more preferably 99.99% by mass or more. Not limited
  • the copper which is the main component of the sputtering target of the present invention includes not only oxygen-free copper (99.96% or more of high purity copper) but also tough pitch.
  • the sputtering target preferably has an average crystal grain size of at least 200 ⁇ m or less, for example, on the sputtering surface, but the average crystal grain size on the sputtering surface is not particularly limited.
  • the sputtering target of the present invention is not limited in its shape such as, for example, a cylindrical shape, a plate shape, and a strip shape.
  • the target of the present invention is not particularly limited also for the method of manufacturing the same. That is, the adjustment method for setting the content of sulfur (S) to 10 ppm or less and the content of lead (Pb) to 2 ppm or less is not particularly limited.
  • sulfur (S) and lead (Pb) are removed as much as possible at the time of copper refining, and then, when casting an ingot, sulfur (S) and lead (Pb) are intentionally added to form sulfur (S) And lead (Pb) can be adjusted to be in a range satisfying the predetermined weight% concentration or less.
  • the method for removing sulfur (S) and lead (Pb) at the time of copper refining is not limited either, but for example, sulfur (S) blows oxygen, for example, desulfurizes it, and then removes it. It can be removed when acidifying to produce oxygen free copper.
  • Lead (Pb) can be removed by, for example, electrorefining, but can be removed by using a zone melting method (zone melting method) or the like if higher purification of copper is desired.
  • the present invention it is possible to provide a sputtering target in which the occurrence of splash is prevented during sputtering of a target, and the uniformity of the film thickness of a thin film formed by sputtering is improved.
  • the sputtering target in this embodiment is mainly composed of copper having a purity of 99.9 (3N) mass% or more, and contains 10 ppm or less of sulfur (S) and 2 ppm or less of lead (Pb).
  • chemical components such as bismuth (Bi), selenium (Se), and tellurium (Te) are contained at an appropriate mass% concentration.
  • the sputtering target has a cylindrical shape in which at least the average crystal grain size of the sputtering surface is 200 ⁇ m or less, and the outer diameter is 150 mm or more and the thickness is 20 mm or more, for example.
  • the manufacturing method of the sputtering target mentioned above is demonstrated below.
  • a copper mat mainly from which iron is removed is obtained as an intermediate product of copper refining.
  • the copper mat is put into a converter and oxygen is blown to oxidize and remove impurities such as sulfur, thereby refining crude copper (having a copper content of about 98%).
  • crude copper having a copper content of about 98%).
  • the crude copper can be refined to 99.99% or more pure copper by electrorefining in a nitric acid bath or a sulfuric acid bath.
  • the ingot is cut into a predetermined size to produce a billet for hot working.
  • a billet with a diameter of 300 mm and a weight of 300 kg to 400 kg is produced.
  • the billet as a material for hot working can be made into other shape suitable for subsequent processing operations, such as plate shape, etc., it is cylindrical to obtain a cylindrical sputtering target. It is formed in.
  • a sputtering target is created using the billet for hot extrusion mentioned above through a hot working process, a cold working, and a strain removal annealing process in this order.
  • hot working it is a step of performing appropriate working such as hot extrusion, hot pressing, hot forging, or hot rolling on a billet made of high purity copper, for example.
  • the hot working is applied at a predetermined working amount so as to strain the billet by the hot working.
  • the amount of processing is appropriately defined as a ratio of the ratio of the reduction in thickness (reduction amount) to the initial thickness multiplied by 100%, or the amount of shear strain.
  • the billet for hot working is previously brought to a temperature exceeding 500.degree. C. and preparation for hot working is prepared. Hot extrusion.
  • the subsequent cold working is a step of performing appropriate working of, for example, cold rolling, cold forging, and cold extrusion on a hot worked material, and cold working is performed by, for example, cold rolling
  • the hot-worked material is cooled to about room temperature at a cooling rate of 80 to 120 ° C./sec, and at least one cold drawing per cylindrical hot-worked material under atmospheric conditions.
  • the diameter is reduced with a diameter reduction rate that gives a strain of at least%, and processed into a target material of a desired final thickness.
  • the diameter reduction ratio can be defined as a ratio of the ratio of the amount of reduction (thickness reduction) to the initial thickness multiplied by 100%, or the amount of shear strain.
  • the strain removing annealing step is effective in that the internal stress causing the strain can be removed.
  • the annealing temperature is too low, recrystallization will not occur, and if the annealing temperature is too high, excessive grain growth will occur. Therefore, for example, an appropriate annealing temperature of 250 ° C. or higher should be set in consideration of these. There is a need.
  • a sputtering target containing copper as a main component having a purity of 99.9% by mass or more and containing 10 ppm or less of sulfur (S) and 2 ppm or less of lead (Pb) can be manufactured.
  • the heat generated when the hot working process is performed on the billet mentioned above causes the crystal grain size of the billet to increase and causes surface roughening such as cracking, but this is caused by adding sulfur (S) conventionally. It is known that the effect of preventing such phenomena can be obtained. On the other hand, it is also known that if sulfur (S) is added too much, for example, to 18 ppm or more, there is an adverse effect that a delicate crack occurs in the structure.
  • the number of occurrences of arcing generated from the target can be reduced, generation of coarse clusters such as splash can be prevented, and uniformity of the film thickness of a thin film formed by sputtering can be improved.
  • the substrate size becomes larger, for example, the substrate size becomes larger than 2 m, and along with this, the large substrate It is necessary to form a film on a wafer or a wafer.
  • the sputtering target itself to be used also increases in size, and the structure of copper tends to be uneven at each site of the sputtering target material, which has a problem that the influence on the film thickness accuracy and the generation of coarse clusters becomes large. .
  • the content of sulfur (S) is 10 ppm or less
  • the content of lead (Pb) is set to 2 ppm or less
  • Sputtering is performed using a DC magnetron sputtering apparatus under the conditions of an ultimate vacuum of 4 ⁇ 10 -5 Pa, an argon pressure of 0.3 Pa, and an oxygen partial pressure of 1 ⁇ 10 -3 Pa as sputtering conditions.
  • the power amount was set to 2 W / cm 2 .
  • board thickness is 30 mm is used.
  • the target of the conventional example is a chemical component contained in the target and an oxygen-free copper for an electron tube whose content satisfies the standard of JIS H3100-C1020.
  • the targets of the conventional example are those in which sulfur (S) is 18 ppm or less, lead (Pb) is 10 ppm or less, bismuth (Bi) is 3 ppm or less, and tellurium (Te) is 5 ppm or less.
  • the main component is copper having a purity of 99.9% by mass or more.
  • the conventional target has a sulfur (S) content of 10 ppm or less, but a lead (Pb) content of more than 2 ppm, and a lead (Pb) content of 2 ppm or less.
  • the content of (S) is greater than 10 ppm, or the content of sulfur (S) is greater than 10 ppm, and the content of lead (Pb) is greater than 2 ppm.
  • the targets of the conventional example a total of six types of samples of the conventional examples 1 to 5 and the comparative example were prepared, and as shown in Table 1, the contents of sulfur (S) and lead (Pb) For Conventional Example 1 at 15 ppm and 5 ppm, Conventional Example 2 at 15 ppm and 2 ppm, Conventional Example 3 at 15 ppm and 1 ppm, Conventional Example 4 at 10 ppm and 5 ppm, and Conventional Example 5 at 5 ppm and 5 ppm. Comparative examples are 8 ppm and 5 ppm.
  • the target of the comparative example uses the thing of the same chemical composition as the copper ingot which concerns on the Example disclosed in "patent 3975414".
  • the target of the example is mainly composed of copper having a purity of 99.9% by mass or more, and contains 10 ppm or less of sulfur (S) and 2 ppm or less of lead (Pb).
  • Example 1 is 10 ppm and 2 ppm
  • Example 2 is 10 ppm and 1 ppm
  • Example 3 is 5 ppm and 2 ppm
  • Example 4 is 5 ppm and 1 ppm.
  • Table 1 shows the contents of sulfur (S) and lead (Pb) for each of the conventional example, the comparative example, and the examples, and as the experimental results to be described later, for each of the conventional examples and the examples The number of cracks on the target surface and the number of arcings generated during the sputtering process are shown.
  • the number of cracks [pieces / 100 mm 2 ] indicates the number of cracks in the inspection area 100 mm 2 of the surface (or cross section) of the sputtering target, and the number of arcings is 30 mm in thickness of the plate-like target material Indicates the number of occurrences of arcing that occurred when sputtering was performed to 20 mm, that is, to 10 mm in the thickness direction (depth direction).
  • the number of arcing generated during the sputtering process was measured using an arcing counter.
  • a data collector manufactured by LANDMARK TECHNOLOGY was used as the arcing counter.
  • As a measure of the number of arcing times it is considered that when the number of arcing times exceeds 30, an increase in the product loss rate due to an increase in the abnormal film formation location with respect to the electrode etc. on the counter substrate is noticeable.
  • FIG. 1 shows the concentration of sulfur (S) and lead (Pb) in each of Examples 1 to 4 and Conventional Examples 1 to 5 when the content (ppm) of sulfur (S) is plotted on the horizontal axis. It is a graph which shows a relation with the number of cracks [piece / 100 mm 2 ].
  • FIG. 2 shows the concentration and cracking of sulfur (S) and lead (Pb) in each of Examples 1 to 4 and Conventional Examples 1 to 5 when the content (ppm) of lead (Pb) is plotted on the horizontal axis. It is a graph which shows a relation with number [piece / 100 mm 2 ].
  • FIG. 3 is a graph showing the relationship between the number of cracks and the number of occurrences of arcing in each of Examples 1 to 4 and Conventional Examples 1 to 5.
  • the size of the crack which is the range that affects the occurrence of arcing.
  • variety (the opening of a weir) of a weir is defined as a crack, and is counted.
  • the crucible shown in FIG. 4 (a) is a crucible having a width of at most 0.3 mm
  • FIG. 4 (b) is a crucible having a width of at most 0.004 mm. Since the diameter is .003 mm or more, these ridges are included in the definition of cracks in the present embodiment.
  • the length of the ridge in FIG. 4 (a) is 3.34 mm in the longitudinal direction, and the length of the ridge in FIG. 4 (b) is 0.031 mm in the longitudinal direction.
  • the crucible shown in FIG. 5 has a width smaller than 0.003 mm and a width equal to that of the grain boundary, and therefore is not included in the definition of the crack.
  • the width of the ridge is smaller than 0.003 mm, the length of the ridge in the longitudinal direction may be arcing even if it is longer than, for example, 4 mm as shown in FIG.
  • the weir as shown in FIG. 5 is not included in the definition of the crack in the present embodiment.
  • the number of cracks on the surface of the sputtering target is 50 [pieces] in each of Conventional Examples 1 to 5 and Comparative Example. It became more than / 100mm 2 ]. On the other hand, in the case of Examples 1 to 4, it was confirmed that all were 50 [pieces / 100 mm 2 ] or less.
  • the sputtering target is mainly composed of copper having a purity of 99.9% by mass or more, and a content of sulfur (S) of 10 ppm or less, and lead (Pb)
  • S sulfur
  • Pb lead
  • the sputtering target which can aim at improvement of the film-forming speed
  • the sputtering method is a film forming method for forming a thin film having the same composition as the sputtering target on the object to be sputtered, as described above. In such sputtering method, production is performed to reduce the cost of the final product.
  • throughput throughput
  • the deposition rate at the time of sputtering depends on the sputtering conditions such as gas pressure, input power, and the distance between the target and the substrate.
  • These sputtering conditions include thin films such as film thickness uniformity as well as deposition rate. If the film thickness uniformity is impaired by setting the sputtering conditions only from the viewpoint of improving the deposition rate, for example, the electric resistance may increase or particles may be affected. In some cases, coarse clusters such as splash and dust occur.
  • the increase of the electrical resistance causes the delay of the processing signal, and the occurrence of coarse clusters may cause a disconnection problem. That is, in order to improve the deposition rate at the time of sputtering while maintaining the quality of the thin film, there is a limit to the examination of the sputtering conditions alone.
  • Prior art document 1 consists of high purity copper of at least 99.999%, an average particle size of 10 to 30 ⁇ m, and contains (111), (200), (220) and (311) orientations, A method of processing a copper sputter target is disclosed in which the amount of particles having each of the orientations is less than 50 percent crystal orientation, and using such a copper sputter target to sputter a film with excellent uniformity to the wafer It is disclosed that can be
  • the sputtering characteristics change depending on the crystal orientation of the sputtering, the crystal grain size, the purity of copper, etc. Therefore, as various researches and developments focused on this point are performed, a lower electrical resistance than before is secured. However, the effect of improving the deposition rate has been raised to a certain extent.
  • the substrate size becomes larger than 2 m.
  • the sputtering target itself to be used also becomes large, the structure of copper tends to be non-uniform for each part of the sputtering target material, and the influence on the film thickness accuracy and the generation of coarse clusters is increased.
  • Such a sputtering target is a sputtering target made of high purity copper having a purity of 99.9% (3 N) or more, and the Miller index of the crystal structure on the sputtering surface to be sputtered is (111), (200) I (111), I (200), I (220), and I (311), which are peak intensities of X-ray diffraction of each orientation plane represented by plane, (220) plane, and (311) plane [Equation 1] I (111) / [I (111) + I (200) + I (220) + I (311)] ⁇ 0.40 ,and, [Equation 2] I (111)> I (200), I (111)> I (220), I (111)> I (311) The crystal orientation is satisfied.
  • the sputtering target is [Equation 1 '] I (111) / [I (111) + I (200) + I (220) + I (311)] ⁇ 0.55 It is more preferable that the crystal orientation satisfies
  • the crystal orientation ratio in which the (111) plane is the largest among the (111) plane, the (200) plane, the (220) plane, and the (311) plane and can do.
  • the atomic density in the FCC metal such as copper is the highest among the four orientation planes described above in the (111) plane, and the (111) plane is the closest.
  • the orientation ratio of the (111) plane ([several 1 L]) to 40% or more, as in the relationship of [Equation 1], from the surface of the sputtering target , Can fly more copper atoms.
  • the orientation ratio of [Equation 1 L], that is, the (111) plane is made use of the characteristic that the above-described (111) plane has a higher emission density of copper atoms than other orientation planes. Can be 40% or more.
  • the deposition rate can be improved.
  • a copper film having a uniform film thickness can be formed by closely discharging a large number of copper atoms from the surface of the sputtering target, and low electrical resistance can be ensured.
  • the signal processing can be speeded up and high reliability can be realized while the final product is improved by throughput. Cost reduction can be achieved.
  • the denominator of [Equation 1 L] is the sum of the peak intensities of the X-ray diffractions of the four orientation planes as in [I (111) + I (200) + I (220) + I (311)]. , For the following reasons.
  • the (200) plane can be made the second highest crystal orientation ratio next to the (111) plane among the orientation planes.
  • the (200) plane is second after the (111) plane. Since the atomic density is high, copper atoms can be ejected relatively densely as compared with the (220) plane and the (311) plane.
  • copper atoms can be densely ejected from the surface of the sputtering target together with the (111) plane, so that the film forming speed can be improved, and a uniform film thickness with low electric resistance can be formed.
  • the (200) plane can be ejected from the surface of the sputtering target with low energy because the atomic density is lower than the (111) plane, the crystal orientation ratio of only the (111) plane is As compared with the case where the temperature is increased, the energy of popping out of copper atoms can be suppressed as a whole as a whole, which can lead to the reduction of the voltage at the time of sputtering (hereinafter referred to as "sputtering voltage").
  • the (111) plane can scatter copper atoms densely, while the (200) plane can not scatter copper atoms more densely than the (111) plane. However, it has the property that it is possible to keep the fly out energy of copper atoms low.
  • the sputtering target is [Equation 4] I (200) ⁇ 0.42 ⁇ I (111)
  • the (111) plane with the highest crystal orientation ratio can be used so that the characteristics of the (111) plane and the (200) plane can be utilized.
  • the crystal orientation rate of the (200) plane can also be made higher than other orientation planes.
  • the crystal orientation ratio is increased compared to other orientation planes only in the (111) plane, as compared with the case where the crystal orientation rate is increased. And the popping out energy (sputtering voltage) can be suppressed low.
  • the sputtering target is characterized in that the grain size of crystal grains is 65 to 200 ⁇ m.
  • the sputtering target requires high energy to fly copper atoms from the surface of the target when the grain size of the crystal grain is large. Therefore, by setting the grain size of the crystal grains to a small value range of 65 to 200 ⁇ m, the energy for causing the copper atoms to fly away from the target surface can be suppressed low.
  • the (111) or (200) plane which is an orientation plane that requires high energy to cause copper atoms to fly away from the target surface, is oriented at a high orientation rate. Setting the grain size of crystal grains to a small value range is particularly effective in reducing the energy for causing copper atoms to fly off the target surface.
  • the sputtering target so that the grain size of the crystal grains is in the range of a smaller value of 65 to 160 ⁇ m.
  • the energy for causing the copper atoms to fly away from the target surface can be further reduced compared to when the range of the grain size of the crystal grains is set to 65 to 200 ⁇ m.
  • an ordinary ingot is electrorefined in a nitric acid bath or a sulfuric acid bath, vacuum induction melting of copper with reduced content of impurities as much as possible is performed, and an ingot made of high purity copper of 99.9% (3N) or more Get The ingot is cut to a predetermined size to make a billet for hot working.
  • a sputtering target is created using the billet for hot extrusion mentioned above through a hot extrusion process, cold working, and an annealing process in this order.
  • the billet for hot working is previously prepared to be hot worked by setting the temperature to over 500 ° C., and the hot extrusion is preferably performed at 500 to 900 ° C., more preferably Hot extrusion at 660-800 ° C. Thereafter, in cold working, cooling is performed to about room temperature at a cooling rate of 50 ° C./s or more, more preferably 80 ° C./s to 120 ° C./s.
  • copper recrystallization is performed, for example, at a temperature of 250 ° C. to 400 ° C., more preferably 300 ° C. to 400 ° C. If the temperature is too low, recrystallization will not occur, and if the temperature is too high, overgrowth of grains may occur. Since the strain inherent in the copper material affects the protrusion of the target material, it is effective to remove the internal stress that causes the strain by performing the annealing process, and the internal stress is removed by the annealing process. be able to.
  • the film forming speed can be further improved, and a large film thickness with low electrical resistance can be formed by closely flying many copper atoms from the surface of the sputtering target.
  • the sputtering targets of Examples 5 to 10 and Comparative Examples 1A and 2A are each made of a copper material having the purity shown in Table 2.
  • the sputtering targets of Comparative Examples 1A and 2A are manufactured by a general manufacturing method conventionally performed, and in detail, an ingot made of high purity copper is subjected to hot working such as hot rolling or hot pressing, Subsequently, after cold working such as cold rolling is performed, heat treatment is finally performed to manufacture, but in hot rolling, for example, heating is performed to a temperature of 930 °, etc. It carried out under the conventional manufacturing conditions different from Examples 5-10.
  • the target materials of Examples 5 to 10 were manufactured under the manufacturing conditions for manufacturing the sputtering target of the present embodiment described above, by performing the hot extrusion process, the cold working process, and the annealing process in this order.
  • the sputtering targets of Examples 5 to 10 and Comparative Examples 1A and 2A are all manufactured through the above-described steps, and used in a state of being additionally processed into a desired target shape by arbitrary machining such as a lathe.
  • the orientation ratio of the (111) plane of these sputtering targets, the average crystal grain size, and the film electrical resistivity are as shown in Table 2.
  • the sputtering targets of Comparative Examples 1A and 2A are smaller than 40%, while the sputtering targets of Examples 5 to 10 are produced by the manufacturing method of the present embodiment described above.
  • the sputtering targets of Examples 5 to 8 are all 40% or more, and the sputtering targets of Examples 9 and 10 are both 55% or more.
  • the average grain size, the grain size in the copper material plate in each of the above-mentioned parts, perform microstructural observation on the surface used as a sputtering target, and the grain size based on JIS H 0501 (cutting method) It measured and calculated based on this.
  • Sputtering is carried out on a 0.7 mm thick OA-10 glass substrate manufactured by Nippon Electric Glass Co., Ltd. using a sputtering target prepared as described above, using a DC magnetron sputtering apparatus, and a 0.3 ⁇ m film is formed. A thick copper wire was created.
  • the sputtering conditions were such that the Ar gas pressure was 0.3 Pa and the discharge power was 500 W.
  • Comparative Examples 1A and 2A are 2.1 [ ⁇ cm] and 2.2 [ ⁇ cm], respectively, while Examples 5, 6, and 8 to 10
  • the values were 2.2 [ ⁇ cm], 2.2 [ ⁇ cm], 2.1 [ ⁇ cm], 2.1 [ ⁇ cm] and 2.0 [ ⁇ cm], which were substantially the same as these values, respectively.
  • Example 7 it was 1.8 [ ⁇ cm], which was a lower value than in the cases of Comparative Examples 1A and 2A.
  • Example 7 is made of high purity copper having a purity of 5 N (99.999%) or higher, and it is considered as a factor that the average grain radius is smaller than that of the other sputtering targets. .
  • Comparative Examples 1A and 2A are both 8 [ ⁇ / s], whereas in Examples 5 to 10, 12 [ ⁇ / s] and 11 [ ⁇ ]. / S], 12 [ ⁇ / s], 10 [ ⁇ / s], 14 [ ⁇ / s], 15 [ ⁇ / s], which were faster than those of Comparative Examples 1A and 2A.
  • the speed was significantly faster than in Examples 5 to 8.
  • the sputtering target of the present embodiment is not limited to the above-described embodiment, and can be manufactured by various embodiments and manufacturing methods.
  • I (111), I (200), I (220), and I (311) are, for example, the relationship of [Equation 3], that is, I (200)> I (220) It is preferable that the relationship of I (200)> I (311) is satisfied, but as long as the relationship of [Equation 1] and [Equation 2] is satisfied, a configuration that does not necessarily satisfy the relationship of [Equation 3] Also included.
  • I (111), I (200), I (220), and I (311) have, for example, the relationship of [Equation 4], that is, I (200) ⁇ 0.42 It is preferable to satisfy the relationship of ⁇ I (111), but as long as the relationship of [Equation 1] and [Equation 2] is satisfied, it also includes a configuration that does not necessarily satisfy the relationship of [Equation 4].
  • the present invention is not limited to the above-described embodiment, and can be formed in various other embodiments.

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Abstract

La présente invention a pour objet une cible de pulvérisation qui prévient la formation d'agrégats grossiers tels que des particules, des éclaboussures et de la poussière pendant une pulvérisation d'une cible et qui améliore l'uniformité de l'épaisseur d'une couche mince formée par pulvérisation. La cible de pulvérisation est principalement composée de cuivre d'une pureté supérieure ou égale à 99,9 % en masse. La cible de pulvérisation est caractérisée en ce qu'elle contient 10 ppm ou moins de soufre (S) et 2 ppm ou moins de plomb (Pb) et elle est de préférence caractérisée en ce que la pureté du cuivre est supérieure ou égale à 99,96 % en masse.
PCT/JP2013/056231 2012-03-09 2013-03-07 Cible de pulvérisation WO2013133353A1 (fr)

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WO2018117717A1 (fr) * 2016-12-23 2018-06-28 희성금속 주식회사 Procédé de prédiction de la vitesse de dépôt d'une cible de pulvérisation, cible de pulvérisation à vitesse de dépôt réglée et son procédé de fabrication
KR102560279B1 (ko) * 2020-11-10 2023-07-27 오리엔탈 카퍼 씨오., 엘티디. 스퍼터링법을 이용한 박막 코팅용 열간 압출 기술로 구리 원통형 타겟을 제조하는 방법

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JPH10330923A (ja) * 1997-06-02 1998-12-15 Japan Energy Corp 高純度銅スパッタリングタ−ゲットおよび薄膜
JP2001152266A (ja) * 1999-11-22 2001-06-05 Kobe Steel Ltd 熱間加工性に優れた銅または銅合金鋳塊

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JP3713332B2 (ja) * 1996-06-21 2005-11-09 同和鉱業株式会社 単結晶銅ターゲット及びその製造方法
JP4118814B2 (ja) * 2002-01-30 2008-07-16 日鉱金属株式会社 銅合金スパッタリングターゲット及び同ターゲットを製造する方法
US20100000860A1 (en) * 2006-09-08 2010-01-07 Tosoh Smd, Inc. Copper Sputtering Target With Fine Grain Size And High Electromigration Resistance And Methods Of Making the Same
JP5092939B2 (ja) * 2008-07-01 2012-12-05 日立電線株式会社 Ｔｆｔ用平板型銅スパッタリングターゲット材及びスパッタリング方法
CN102482767B (zh) * 2009-08-28 2014-05-07 古河电气工业株式会社 溅射靶用铜材料及其制造方法

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JPH1060632A (ja) * 1996-08-16 1998-03-03 Dowa Mining Co Ltd スパッタリングターゲット及びその製造方法ならびに半導体素子
JPH10330923A (ja) * 1997-06-02 1998-12-15 Japan Energy Corp 高純度銅スパッタリングタ−ゲットおよび薄膜
JP2001152266A (ja) * 1999-11-22 2001-06-05 Kobe Steel Ltd 熱間加工性に優れた銅または銅合金鋳塊

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