Patent Application
20130228566
The present indention relates to an apparatus of heating semiconductors.
In a system of producing semiconductors used far dry process or plasma coating in semiconductor production, it has been used halogen-based plasma such as F, Cl or the like Easing high reactivity for etching or cleaning. It is thus required, for a member equipped to suck semiconductor production system, high corrosion resistance, so that it has been generally used a member of an anti-corrosive metal such as aluminum with alumite treatment, HASTELLOY or the like or a ceramic material. Especially, it is necessary high corrosion resistance and low particle generation properties for an electrostatic chuck or heater member supporting and fixing a Si wafer, so that it has bees used a high corrosion resistant ceramic member such as aluminum nitride, alumina, sapphire or the like. As these materials are used for a long time, they are gradually corroded to induce particle generation, so that it has been demanded a material whose corrosion resistance is further improved. For attending such demands, it is studied to use, as the material, magnesia, spinel (MgAl2O4) or a composite material thereof whose corrosion resistance is higher than that of alumina (For example, Patent document 1: U.S. Pat. No. 3,559,426B).
It is further known a ceramic heater used for heating wafers. In such ceramic heaters, temperature uniformity of the heater is required for heating the wafer uniformly. For example, according to the disclosure of Patent Document 2 (Patent Publication No. H08-073280A), a heat resistance is embedded in an aluminum nitride based ceramic plate, to which an aluminum nitride based shaft is bonded to provide a ceramic heater. According to the descriptions of Patent document 3 (Patent Publication No. 2003-288975A), in a ceramic heater with a shaft, a content of metal carbide in a heat resistance is lowered to reduce the deviation of the carbide content in the heat resistance depending on the positions, so that the temperature distribution on its heating face is reduced.
Usually, in semiconductor production process, a corrosive gas such as halogen based gas or the like is used for cleaning of a system for preventing contamination of a wafer. Further, it is required temperature uniformity on the wafer for forming a film uniformly on the wafer. As a member of holding and further heating an Si wafer in a semiconductor production system, it has been widely used a ceramic heater made of AlN (aluminum nitride) as exiting art, resulting in good temperature uniformity on the wafer in initial stage. However, AlN is corroded fey cleaning with the corrosive gas, so that the shape and roughness of the surface of the heater are changed and the temperature distribution is thereby changed during its use life. It is problematic that the temperature uniformity cannot be maintained.
An object of the present invention is, in a ceramic heating apparatus used for processing semiconductors, to reduce particles when the apparatus is used under halogen corrosive gas or its plasma atmosphere, and to maintain good temperature uniformity for a long period of time.
The present invention provides a heating apparatus comprising a susceptor comprising a heating face of heating a semiconductor. The susceptor comprises a plate shaped main body and a surface corrosion resistant layer for facing said heating face, and the surface corrosion resistant layer comprises a ceramic material comprising main components comprising magnesium, aluminum, oxygen and nitrogen, and the ceramic material comprises a main phase comprising magnesium-aluminum oxynitride phase exhibiting an XRD peak at least in 2θ=47 to 50° taken by using CuKα ray.
The ceramic material of the present invention includes the Magnesium-aluminum oxynitride phase as its main phase, and is superior in corrosion resistance against strong corrosive gas such as halogen based gas, compared with aluminum nitride. By forming the surface corrosion resistant layer of the susceptor with such ceramic material, the surface state is not susceptible to change by the corrosion when it is used for a long time under corrosive condition. As a result, it becomes possible to maintain good temperature uniformity on a wafer for a long time.
Further, it is possible to form the plate shaped main body with a different material having a thermal conductivity higher than that of the ceramic material. It is thereby possible to facilitate thermal conduction in planar direction on the susceptor so that the temperature uniformity on the wafer can be further improved.
The patent or application file contains at least one drawing executed in color. Copies of this patent or patent application publication with color drawing(s) will be provided by the Office upon request and payment of the necessary fee.
The novel ceramic material used in the present invention will be described first, and details of the heating apparatus will be described later.
The inventors intensively studied corrosion resistance of a ceramic material produced by molding a mixture of magnesium oxide, alumina and aluminum nitride powders and by sintering the mold by hot press sintering. As a result, it was found that considerably high corrosion resistance can be obtained by the ceramic material including a main phase composed of magnesium-aluminum oxynitride having an XRD peak at a specific position.
That is, the inventive ceramic material comprises main components comprising magnesium, aluminum, oxygen and nitrogen, and the ceramic material comprises a main phase comprising magnesium-aluminum oxynitride phase exhibiting an XRD peak at least in 2θ=47 to 50° taken by using CuKα ray.
The ceramic material of the present invention has corrosion resistance comparable with, or superior than, that of spinel. Therefore, the inventive susceptor can endure against halogen based plasma such as F, Cl or the like used in a semiconductor production process for a long time, so that it is possible to reduce an amount of particles generated from the susceptor member. Moreover, even when the susceptor is used for a long time under corrosive condition, the change of the surface state due to corrosion can be reduced, so that it is possible to obtain good temperature uniformity on a wafer for a long time.
The inventive ceramic material includes main components including magnesium, aluminum, oxygen and nitrogen, and the ceramic material includes a main phase comprising the magnesium-aluminum oxynitride phase exhibiting an XRD peak at least in 2θ=47 to 50° taken by using CuKα ray. As the magnesium-aluminum oxynitride has corrosion resistance against halogen based plasma comparable with, or superior than, that of spinel, it is considered that the inventive ceramic material including the oxynitride as its main phase also exhibits high corrosion resistance. Further, the magnesium-aluminum oxynitride has corrosion resistance comparable with that of spinel, and at the same time, can have a linear thermal expansion coefficient lower than that of spinel.
The inventive ceramic material may contain, as a sub phase, crystal phase of MgO—AlN solid solution composed of magnesium oxide to which aluminum nitride is dissolved. The MgO—AlN solid solution is also anti-corrosive, so that it is not problematic if it is contained as a sub phase. The XRD peaks at (200) and (220) faces of the MgO—AlN solid solution taken by using CuKα ray may be observed in ranges of 2θ=42.9 to 44.8° and 62.3 to 65.2° respectively which are between peaks of cubic phase of magnesium oxide and cubic phase of aluminum nitride, respectively. Further, XRD peak at (111) face may be observed in a range of 2θ=36.9 to 39°, which is between peaks of cubic phase of magnesium oxide and cubic phase of aluminum nitride. Since it may be difficult to distinguish the peak at (111) face from the peaks corresponding with the other crystalline phases, only the XRD peaks at (200) face and (220) face may be observed in the above ranges. Similarly, it may be difficult to distinguish the peak at (200) face or the peak at (220) face from the peaks corresponding with the other crystalline phases.
In the inventive ceramic material, for obtaining corrosion resistance comparable with, or higher than, that of spinel, the content of AlN crystal phase may preferably be lower and more preferably AlN crystal phase is not contained, because the corrosion resistance tends to be deteriorated in the case that AlN crystal phase is contained as the sub phase. Further, since the corrosion resistance of spinel is higher than those of alumina and AlN crystals, a small amount of spinel may be contained. However, since the corrosion resistance of spinel is inferior to that of the inventive magnesium-aluminum oxynitride phase or MgO—AlN solid solution, it is preferred that the content of spinel is lower. On the other hand, for lowering the linear thermal expansion coefficient while maintaining the corrosion resistance comparable with that of spinel, a small amount of spinel or AlN crystal phase may be contained.
In the inventive ceramic material, for obtaining corrosion resistance comparable with, or higher than, that of spinel, a molar ratio of magnesium/aluminum in powdery raw material may preferably be 0.20 or higher and 2 or lower, and more preferably be 0.75 or higher and 2 or lower. In the case that the molar ratio of magnesium/aluminum is lower than 0.20, it might be concerned that an amount of generation of either of aluminum nitride, spinel and aluminum nitride would become large to result in reduction of the superior anti-corrosion characteristics. In the case that the molar ratio of magnesium/aluminum exceeds 2, the MgO—AlN solid solution tends to become a main phase. On the other hand, for lowering the linear thermal expansion coefficient while maintaining the corrosion resistance comparable with that of spinel, the molar ratio of magnesium/aluminum in the powdery raw material may preferably be 0.05 or higher and 1.5 or lower, and more preferably be 0.1 or higher and 1 or lower.
An open porosity of the inventive ceramic material may preferably be 5% or lower. Here, the open porosity means a value measured by Archimedean method using pure water as an medium. In the case that the open porosity exceeds 5%, there would be a risk that the strength is lowered or the material itself would become susceptible to removal of grains and the resultant particle generation, and particle components tends to be stored in the pores during the processing of the material, which is not preferred. Further, it is preferred that the open porosity is nearer to zero as possible. The lower limit of it is not particularly defined.
According to the inventive ceramic material, the linear thermal expansion coefficient of the magnesium-aluminum oxynitride forming the main phase in a range of 40 to 1000° C. is 6 to 7 ppm/K. Thus, by changing the ratios of the sub-components such as the MgO—AlN solid solution (12 to 14 ppm/K), spinel (8 to 9 ppm/K), and aluminum nitride (5 to 6 ppm/K), the linear thermal expansion coefficient can be controlled in a range of 5.5 to 10 ppm/K while maintaining the high corrosion resistance. However, since spinel or aluminum nitride is lower in the corrosion resistance than the magnesium-aluminum oxynitride or MgO—AlN solid solution, the contents thereof may be preferably smaller. By adjusting the thermal expansion as such, it is possible to match the thermal expansion with those of aluminum oxide, yttrium oxide and aluminum nitride used for members for semiconductor production systems. Alternatively, the difference of the thermal expansion coefficients can be reduced. By these, it is possible to laminate or adhere the inventive ceramic material onto a prior material. It is thereby possible to use the inventive ceramic material with high corrosion resistance for a surface part (first structural body) and to use the prior material as a base material for a lower part (second structural body). Such layered structure and the adjustment of thermal expansion are particularly effective especially in the co-sintering process. Among them, by using a material mainly composed of aluminum nitride as the base material of the second structural body, it becomes easier to maintain a high thermal conductivity and to maintain the surface temperature uniformity of the ceramic material with high corrosion resistance. Such construction is especially effective in a system of producing semiconductors of so-called heater embedded type.
The inventive ceramic material may be used for a laminated body having a first structural body utilizing the ceramic material and a second structural body including, as its main phase, at least one of aluminum nitride, yttrium oxide and aluminum oxide. Further, it may have a structure in which the first and second structural bodies are laminated or bonded with each other. By applying the first structural body with high corrosion resistance and the second structural body with the other property (for example heat transmission or mechanical strength), it is thereby possible to further improve the corrosion resistance as well as the other properties. Here, the first structural body may be a thin film, plate body or laminated body formed with the ceramic materials. Further, the second structural body may be composed of a thin film, plate-shaped body or laminated body having aluminum nitride, yttrium oxide and aluminum oxide as its main phase. Besides, the bonding may be made according to any embodiment, and for example may be bonded by sintering or an adhesive agent, for example.
At this time, the first and second structural bodies may be bonded with each other through an intermediate layer. By the intermediate layer, it is thereby possible to further prevent the peeling of the first and second structural bodies due to, for example difference of thermal expansion coefficients. The intermediate layer may be a layer having properties between those of the first and second structural bodies. The intermediate layer may be, for example, a layer of mixing the main phases of the first and second structural bodies. Further, the intermediate layer may include a plurality of layers having different components or ratios of components. It is thereby possible to provide properties of a functionally graded material.
Further, a difference of linear thermal expansion coefficients of the first and second structural bodies may be 0.3 ppm or smaller, and the first and second structural bodies may be directly bonded with each other. Since the difference of the linear thermal expansion coefficients of the first and second structural bodies is made thus small, it is possible to avoid the risk of cracks or peeling, in the case that both structural bodies are bonded with each other at a high temperature (for example bonded by sintering) or the laminated body is repeatedly used at high and low temperatures.
The inventive ceramic material can be produced by molding powdery mixture of magnesium oxide, alumina and aluminum nitride and then by sintering. For example, for obtaining high corrosion resistance comparable with, or higher than, that of spinel, 15 mass percent or more and 66.2 mass percent or less of magnesium oxide, 63 mass percent or less of alumina and 57.7 mass percent or less of aluminum nitride may be mixed to obtain powdery mixture, which may be molded and then sintered. Further, 37 mass percent or more and 66.2 mass percent or less of magnesium oxide, 63 mass percent or less of alumina and 57.7 mass percent or less of aluminum nitride may be mixed to obtain powdery mixture, which may be molded and then sintered. On the other hand, for lowering the linear thermal expansion coefficient to improve temperature uniformity while maintaining the corrosion resistance comparable with that of spinel, 5 mass percent or more and 60 mass percent or less of magnesium oxide, 60 mass percent or less of alumina and 90 mass percent or less of aluminum nitride may be mixed to obtain powdery mixture, which may be molded and then sintered. Further, the sintering temperature may preferably be 1750° C. or higher. In the case that the sintering temperature is lower than 1750° C., it would be a risk that the targeted magnesium-aluminum oxynitride would not be generated, which is not preferred. Besides, although the upper limit of the sintering temperature is not particularly limited, it may be 1850° C. or 1900° C., for example. Further, hot press sintering may be preferably applied for the sintering, and a pressure during the hot press sintering may preferably be set in a range of 50 to 300 kgf/cm2. Atmosphere during the sintering may preferably be that which does not affect the sintering of the oxide raw material, and may preferably be an inert atmosphere such as nitrogen, argon, helium atmosphere or the like. The pressure for the molding is not particularly limited and may be adjusted at any pressure as far as it is possible to maintain the shape.
According to a preferred embodiment, the heating apparatus of the present invention includes a susceptor having a heating face for heating a semiconductor and a supporting part joined to a back face of the susceptor.
Susceptors 2 and 12A are plate-shaped, and upper faces 2a and 12a of the susceptors 2 and 12A are semiconductor heating faces. The semiconductor heating faces 2a and 12a are not necessarily flat, and the heating face may be roughened, or it may be formed a groove having a size comparable with that of a substrate or a groove for flowing purge gas. A supporting part 3 is bonded to a lower face (back face) 2b or 12b of the susceptor. According to the present example, the supporting part is tube shaped and a member 5 for supplying electricity is contained inside of the supporting part 3. The member for supplying electricity is connected to a heat resistor 4 embedded within the susceptor.
The susceptor is plate shaped and preferably, substantially circular disk shaped. Although the size of the susceptor is not particularly limited, the diameter is 280 to 380 mm and thickness is 8 to 20 mm, for example. Further, although an outer diameter of a bonding part of the susceptor and supporting part is not particularly limited, the diameter is 60 to 120 mm, for example. It is preferred that the supporting part includes a step therein, a large size part 3a is provided on the side of the susceptor and a small size part 3c is provided on the opposite side with respect to the step. Flanges 3b and 3d are formed on end parts of the large size part 3a and small size part 3c, respectively the flange 3b is not shown in the example of
Here, although the heating member may preferably be embedded within the susceptor, the heating member may be fitted to the susceptor. Alternatively, the heating member may be an outer heating member, such as an infrared ray heating device, fitted at a position distant from the susceptor.
Here, according to the comparative example shown in
Further, according to a heating apparatus 11B shown in
Further, according to a heating apparatus 11C shown in
Further, according to a heating apparatus 11D shown in
In the case that a material having a thermal conductivity higher than that of the ceramic material is used as a material of the plate shaped main body, the temperature uniformity on wafer is improved due to the thermal conduction in the plate shaped main body as a whole. However, in this case, since an amount of heat radiation from the back face 13b of the plate shaped main body 13 is also increased, there is a possibility that the temperature uniformity on wafer may be deteriorated due to uneven thermal radiation. According to the present embodiment, since the back face covering layer made of the ceramic material is provided on the side of the back face of the plate shaped main body, it is possible not only to realize the corrosion resistance on the side of the back face, but also to reduce the thermal radiation from the back face of the susceptor as a whole so that the temperature uniformity on wafer can be further improved.
According to the present invention, although the susceptor is formed of the ceramic material, a material forming the supporting part 3 (so called shaft) is not particularly limited and includes the followings.
The ceramic material of the present application, aluminum nitride, alumina, magnesium oxide, spinel
Preferably, the material of the supporting part 3 is made the ceramic material described above. Even in this case, however, the ceramic materials forming the susceptor and supporting part is not necessarily identical and may be of compositions different from each other in the composition range as described above.
A wire conductor may be bent and processed to a wounded body, which may be used as the heating member, for example. The wire diameter of the heating member is about 0.3 to 0.5 mm, and the winding diameter in the case of a coil shaped member is about 2 to 4 mm and the pitch is about 1 to 7 mm. The “winding diameter” referred to herein means an inner diameter of the coil forming the heating member.
As the shape of the heating member, in addition to the coil shape, various shapes may be applied such as ribbon, mesh, coil spring, sheet, printed electrode or the like. Further, in a part adjoining a through hole formed for supplying purge gas, lift pin or the like, the pattern of the heating member 12 may be optionally changed, for example, the heating member 12 may be turned away from the through hole. As the material of the heating member 12, it may be preferably used a conductive material with a high melting point such as molybdenum (Mo), tungsten (W), niobium (Nb) or the like.
In the susceptor of the heating apparatus, it may be embedded a radio frequency electrode for generating plasma over the susceptor. A material forming the radio frequency electrode may be those described above for the heating member.
According to the inventive ceramic material, the linear thermal expansion coefficient of the magnesium-aluminum oxynitride forming the main phase in a range of 40 to 1000° C. 6 to 7 ppm/K. Thus, by changing the ratios of the sub-components such as the MgO—AlN solid solution (12 to 14 ppm/K), spinel (8 to 9 ppm/K), and aluminum nitride (5 to 6 ppm/K), the linear thermal expansion coefficient can be controlled in a range of 5.5 to 10 ppm/K while maintaining the high corrosion resistance. However, since spinel or aluminum nitride is lower in the corrosion resistance than the magnesium-aluminum oxynitride or MgO—AlN solid solution, the contents thereof may be preferably smaller. By adjusting the thermal expansion as such, it is possible to match the thermal expansion with those of aluminum oxide, yttrium oxide and aluminum nitride used for members for semiconductor production systems. It is thereby possible to laminate or adhere the inventive ceramic material onto a prior material.
Specifically, the materials of the plate shaped main body include aluminum oxide, yttrium oxide, aluminum nitride, magnesium oxide, silicon nitride and spinel, and may particularly preferably be aluminum oxide, yttrium oxide or aluminum nitride.
In particular, by forming the plate shaped main body with a material including aluminum nitride as its main phase, it is possible to maintain high thermal conductivity and easier to maintain the surface temperature of the corrosion resistant ceramic material uniform.
It is not particularly limited a method of bonding the plate shaped main body and each of the corrosion resistant layers and back face covering layer. Both may be bonded with each other by, for example integrated sintering or an adhesive.
Such adhesive includes a silicon based adhesive, acrylic resin based adhesive and Al alloy adhesive.
According to a preferred embodiment, a difference between the thermal expansion coefficient of the plate shaped main body and that of the corrosion resistant layer or the back face covering layer is 0.3 ppm/K or smaller. In this case, when the plate shaped main body and the corrosion resistant layer or back face covering layer are bonded with each other at a high temperature (for example bonded by integrated sintering) or when the laminated body is repeatedly used at high and low temperatures, the risk of cracks and peeling can be avoided.
As described above, the plate shaped main body and each of the corrosion resistant layer and back face covering layer may be bonded through the intermediate layer. It is thereby possible to further prevent the peeling of the corrosion resistant layer and back face covering layer due to the difference of the thermal expansion, for example. The intermediate layer is made a layer whose properties are between those of the plate shaped main body and the corrosion resistant layer or back face covering layer.
Specifically, the intermediate layer may be a composite ceramics obtained by sintering mixture of the ceramic material described above and materials for the plate shaped main body.
Further, the intermediate layer may be composed of a plurality of layers and the compositions of the intermediate layers may be made different form each other to form a graded material layer.
The inventive susceptor is superior in the corrosion resistance against the halogen based corrosive gas and its plasma, and especially excellent in the corrosion resistance against the following halogen based corrosive gasses, the mixtures and plasmas.
NF3, CF4, ClF3, Cl2, BCl3, HBr
Preferred applications of the present invention will be described below. As MgO, Al2O3 and AlN raw materials, they were used commercial products each having a purity of 99.9 mass percent or higher and an average particle size of 1 μm or lower. Here, as about 1 percent of oxygen is inevitable in the AlN raw material, the above described purity is calculated after oxygen content is excluded from the impurity contents. Further, even in the case that it is used MgO material having a purity of 99 mass percent or higher, it could be produced a ceramic material comparable with that produced by using MgO material having a purity of 99.9 mass percent or higher.
First, it will be described the ceramic material containing magnesium, aluminum, oxygen and nitrogen as the main components (Experiments 1 to 19). Besides, the experiments 1 to 3 and 6 to 16 correspond to inventive examples and experiments 4, 5 and 17 to 19 correspond to comparative examples.
Raw materials of MgO, Al2O3 and AlN were weighed according to the mass % shown in table 1, and then wet-mixed using isopropyl alcohol as a solvent, nylon pot and alumina grinding stone with a diameter of 5 mm for 4 hours. After the mixing, slurry was collected and dried in nitrogen flow at 110° C. Thereafter, the dried matter was passed through a sieve of 30 mesh to obtain formulated powder. Besides, the molar ratio of Mg/Al in the formulated powder was 1.2
The formulated powder was subjected to uniaxial press molding at a pressure of 200 kgf/cm2 to produce a disk-shaped molded body haying a diameter of about 35 mm and a thickness of about 10 mm, which was then contained in a graphite mold for sintering.
The disk-shaped body was subjected to hot press sintering to obtain the ceramic material. The hot press sintering was performed at a pressure of 200 kgf/cm2 and at a sintering temperature (the maximum temperature) shown in table 1, in Ar atmosphere until the completion of the sintering. The holding time at the sintering temperature was made 4 hours.
The ceramic material was obtained according to the same procedure as the Experiment 1, except that raw materials of MgO and Al2O3 were weighed according to the mass % shown in table 1.
The ceramic material was obtained according to the same procedure as the Experiment 1, except that the sintering temperature was set at 1650° C.
The ceramic material was obtained according to the same procedure as the Experiment 1, except that raw materials of MgO, Al2O3 and AlN were weighed according to the mass % shown in table 1 and that the sintering temperature was made that shown in table 1.
The ceramic material was obtained according to the same procedure as the Experiment 1, except that raw materials of MgO, Al2O3 and AlN were weighed according to the mass % shown in table 1, that the sintering temperature was made that shown in table 1, and that the atmosphere during the sintering was made N2.
Each of the materials obtained in the experiments 1 to 19 was processed adapted for various evaluation procedures and the following evaluations were performed. The result of each evaluation was shown in table 1. Besides, according to each of the experiments 1 to 19, another sample having a diameter of 50 mm was also produced and it was proved that the samples provided evaluation results similar to those shown in table 1.
They were measured according to Archimedean method using pure water as an medium.
The material was ground using a mortar and its crystal phase was identified by an X-ray diffraction system. The condition of the measurement was made CuKα, 40 kV, 40 mA, and 2θ=5 to 70° C. with a sealed tube type X-ray diffraction system (“D8-ADVANCE” supplied by Bruker AXS corporation) used.
The surface of each of the materials was polished to a mirror face, which was then subjected to corrosion resistance test using an ICP plasma corrosion resistance test system according to the following conditions. The step of a masked face and exposed face was measured by a step gauge and the step value was divided by a test time period to calculate the etching rate of each material.
ICP: 800 W, Bias: 450 W, Introduced gas: NF3/O2/Ar=75/35/100 sccm, 0.05 Torr (6.67 Pa), Exposed time period: 10 hr, Temperature of sample: Room temperature
The detection, identification and analysis of content of each constituent atom were performed using EPMA.
The measurement was performed using a dilatometer (supplied by Bruker AXS corporation) under argon atmosphere.
It was measured by bending strength test according to JIS-R1601.
It was measured a method according to JIS-C2141 in air at room temperature (25° C.). The shape of a test sample was of a diameter of 50 mm×(0.5 to 1 mm), and a main electrode with a diameter of 20 mm, a guard electrode with an inner diameter of 30 mm and an outer diameter of 40 mm and an applying electrode with a diameter of 40 mm were formed, while the electrodes were made of silver. A voltage of 2 kV was applied and it was read a current value at a time point 1 minute after the application of the voltage, and the current value was used to calculate a volume resistivity at room temperature. Further, as to the Experiments 7 and 19 (MgO sintered body), it was measured in vacuum (0.01 Pa or below) and at 600° C. The shape of a test sample was of a diameter of 50 mm×(0.5 to 1 mm), and a main electrode with a diameter of 2 mm, a guard electrode with an inner diameter of 30 mm and an outer diameter of 40 mm and an applying electrode with a diameter of 40 mm were formed while the electrodes were made of silver. A voltage of 500 V/mm was applied and it was read a current value at a time point 1 hour after the application of the voltage, and the current value was used to calculate a volume resistivity. Further, in values of the volume resistivity shown in table 1, “aEb” represents a×10b, and, for example, “1E16” represents 1×1016.
The XRD peaks corresponding with (111) face, (200) face and (220) face of the MgO—AlN solid solution were shown in 2θ=36.9 to 39°, 42.9 to 44.8° and 62.3 to 65.2°, respectively, which are between the peaks of cubic phase of magnesium oxide and cubic phase of aluminum nitride.
Besides, an EPMA element mapping image is divided into colors of red, orange, yellow, yellowish green, green, blue and indigo blue depending on the contents, so that red, indigo blue and black correspond to the highest content, the lowest content and zero, respectively. However, as
Further, according to the Experiment 4, as aluminum nitride was not used, the above described magnesium-aluminum oxynitride was not generated, so that the ceramic material contained, as the main phase, spinel (MgAl2O4). According to the Experiment 5, as the sintering temperature was low, the above described magnesium-aluminum oxynitride was not generated, so that the ceramic material contained magnesium oxide as the main phase and spinel and aluminum nitride as the sub phases.
Then, the etching rates of the ceramic materials of the Experiments 1 to 3 and 6 to 8 were as low as 80 percent or lower, and the etching rates in the Experiments 9 to 12 were as low as 90 percent or lower, of that in the Experiment 4. It was thus proved that the corrosion resistance was very high. As that of the Experiment 5 includes much amounts of spinel and aluminum nitride with lower corrosion resistance, the etching rate was proved to be higher. Besides, the etching rate of alumina shown in the Experiment 18 was higher than that of the ceramic material (spinel) of the Experiment 4. The ceramic materials of the Experiments 1 to 3 and 6 to 8 have sufficiently high bending strengths and volume resistivities.
It was further measured an etching rate at high temperature. Here, for the ceramic materials of the Experiments 2 and 10, the surface of each of the materials was polished to a mirror face and subjected to corrosion resistance test at high temperature under the following conditions using an ICP plasma corrosion resistance test system. Then, a step between the masked face and exposed face measured by a step gauge is divided by a test time period to calculate the etching rate of each material. As a result, the etching rate of each material was ⅓ or lower of that of alumina, ⅕ or lower of that of aluminum nitride, and comparable with that of spinel, and the corrosion resistance against plasma at high temperature was also good.
ICP: 800 W, Bias: none, Introduced gas: NF3/Ar=300/300 sccm, 0.1 Torr, Exposed time: 5 h, Temperature of sample: 650° C.
According to the ceramic materials of the Experiments 12 to 16, the etching rate (212 to 270 nm/h) was very close to that of spinel of the Experiment 4, and the linear thermal expansion coefficient (5.8 to 6.9 ppm/K) was lower than that of spinel. That is, the ceramic materials of the Experiments 12 to 16 were preyed to have corrosion resistance comparable with that of spinel while providing a lower linear thermal expansion coefficient, so that they are useful for materials of an electrostatic chuck and heater, especially heater. Besides, although raw material composition of the Experiment 17 was made identical with that of the Experiment 6, the sintering temperature was made lower. Consequently, its main phase was not the magnesium-aluminum oxynitride but spinel, so that its corrosion resistance was lowered and linear thermal expansion coefficient was higher compared with those of the Experiment 6. Further, the ceramic materials of the Experiments 12 to 16 have sufficiently high bending strength and volume resistivity.
Further, the volume resistivities at 600° C. in the Experiments 7 and 19 were 5×108 Ω·cm and 2×1012 Ω·cm, respectively. It was proved that the ceramic material having, as the main phase, the magnesium-aluminum oxynitride phase having an XRD peak at least in a range of 2θ=47 to 49° (or 47 to 50°) has an electrical resistance lower than that of MgO.
As described above, it is predicted that the ceramic materials produced in the Experiments 1 to 3 and 6 to 16 also have electrical resistances lower than that of magnesium oxide.
Next, it will fee described a laminated body provided fey laminated sintering of first and second structural bodies utilizing the ceramic material described above (Experiments 20 to 26). Besides, the Experiments 20 to 24 correspond to the inventive examples and the Experiments 25 and 26 correspond to comparative examples.
The ceramic materials of the Experiments 4 and 6 to 12 have average linear thermal expansion coefficients of 7 to 9 ppm/K in 40 to 1000° C. According to the Experiments 20 and 21, as shown table 2, the first structural body was made of the ceramic material of the Experiment 10, and the second structural body was made of aluminum nitride. The first and second structural bodies were laminated and molded to a provide a sample having a diameter of 50 mm, which was subjected to laminated sintering. As the aluminum nitride, it was used aluminum nitride to which 5 mass percent of yttrium oxide was added as a sintering aid in outer addition (that is, 5 mass parts of Y2O3 was added to 100 mass parts of AlN, referred to as AlN [1]), or aluminum nitride to which 50 mass percent of yttrium oxide was added (That is, 50 mass parts of Y2O3 was added to 100 mass parts of AlN, referred o as AlN [2]). As raw materials of aluminum nitride and yttrium oxide, it was used commercial products having a purity of 99.9 mass percent or higher and an average particle size of 1 μm or smaller. Here, as AlN material inevitably contains about 1 mass percent of oxygen, the purity was calculated after oxygen is removed from impurity elements. Further, since the average linear thermal expansion coefficient in 40 to 1000° C. was 5.7 ppm/K in AlN [1] and 6.2 ppm/K in AlN[2], it is provided a difference of thermal expansion between the first and second structural bodies. Therefore, between the first and second structural bodies, it was provided an intermediate layer in which the raw materials of AlN[1] or AlN[2] and raw materials of the Experiment 10 were mixed. The difference of thermal expansion can be relaxed by the intermediate layer. In the Experiment 20 using AlN[1], the intermediate layer was composed of three layers having mass ratios of 25:75, 50:50 and 75:25, respectively, and in the Experiment 21 using AlN[2], the intermediate layer was composed of two layers having mass ratios or 40:60 and 60:40, respectively. It will be described steps of formulation, molding and sintering below in detail.
As the raw material of the first structural body, it was used formulated powder produced according to the similar procedure as the Experiment 10 described above. The raw material of the second structural body was produced as described below with aluminum nitride as the main phase. In AlN [1] of the second structural body, first, aluminum nitride powder and yttrium oxide powder were weighed in a ratio of 100 mass percent and 5.0 mass percent, and then wet-mixed using isopropyl alcohol as a solvent, a nylon pot and nylon agitating media for 4 hours. After the mixing, slurry was collected and dried in nitrogen flow at 110° C. Thereafter, it was passed through a sieve of 30 mesh to produce formulated powder. Further, the thus obtained formulated powder was thermally treated at 450° C. for 5 hours or longer in air atmosphere to fire and remove carbon contents included during the wet mixing. The intermediate layer of the laminated body using AlN[1] was formulated as follows. First, the formulated powders of the Experiment 10 and aluminum nitride described above were weighed in mass ratios of 75:25 (intermediate layer 1), 50:50 (intermediate layer 2), and 25:75 (intermediate layer 3), and then wet-mixed using isopropyl alcohol as a solvent, a nylon pot and nylon agitating media for 4 hours. After the mixing, the slurry was collected and then dried in nitrogen flow at 110° C. Thereafter, it was passed through a sieve of 30 mesh to provide formulated powder. AlN[2] of the second structural body was produced according to the same procedure as AlN[1], except that the aluminum nitride powder and yttrium powder were mixed in a ratio of 100 mass percent and 50 mass percent, respectively. Further, the intermediate layer of the laminated body using AlN[2] was formulated according to the same procedure as AlN[1], except that the formulated powder of the Experiment 10 and that of the aluminum nitride described above were mixed in mass ratios of 60:40 (intermediate layer 1) and 40:60 (intermediate layer 2), respectively.
First, the aluminum nitride formulated powder as the raw material of the second structural body was filled in a metal mold having a diameter of 50 mm, and molded by uniaxial pressure molding at a pressure of 200 kgf/cm2. The aluminum nitride molded body was not drawn out of the mold, and formulated powders of the intermediate layers were filled thereon in the descending order of aluminum nitride contents, while a pressure of 200 kgf/cm2 was applied after each of the filling procedure by uniaxial pressure molding. Lastly, the formulated powder of the Experiment 10 as the raw material of the first structural body was filled and then pressure molded at a pressure of 200 kgf/cm2. As to the laminated body using AlN[1], it was prepared a disk-shaped molded body having a total thickness of 23 mm and including an aluminum nitride layer of 10 mm as the second structural body, three intermediate layers each having a thickness of 1 mm and the layer of the Experiment 10 as the first structural body of 10 mm. Further, as to the laminated body using AlN[2], it was prepared a disk-shaped molded body having a total thickness of 22 mm and including an aluminum nitride layer of 10 mm as the second structural body, two intermediate layers each having a thickness of 1 mm and the layer of the Experiment 10 as the first structural body. These laminated and disk-shaped bodies were contained in a graphite mold for sintering.
The disk-shaped molded body contained in the graphite mold for sintering was subjected to hot press sintering to obtain a ceramic material by integrated sintering. The hot press sintering was performed at a pressure of 200 kgf/cm2, a sintering temperature of 1800° C., and in Ar atmosphere until the completion of the sintering. The holding time period at the sintering temperature was made 4 hours. Besides, as to the Experiments 20 and 21, the sintering was also performed at a sintering temperature of 1750° C. (Experiments 20-1 and 21-1).
According to the sintered body obtained in the production method described above, in both of the laminated bodies using AlN[1] (Experiments 20, 20-1) and using AlN[2] (experiments 21 and 21-1), the upper part of the sintered body was composed of the magnesium-aluminum oxynitride with high corrosion resistance, the lower part was composed of a sintered body mainly composed of aluminum nitride with high thermal conductivity and an intermediate layer was provided between them. In the intermediate layer, the Al content was inclined so that the Al content is made higher from the first structural body toward the second structural body. Cracks, fractures or the like were not observed at interfaces of the layers of the sintered bodies. It is considered that thermal stress during the sintering could be avoided fey providing the intermediate layer between the first and second structural bodies. Further, by controlling the thermal expansion coefficient of aluminum nitride as the base material, it is possible to reduce thermal stress generated between the base material and the magnesium aluminum oxynitride and thereby to reduce the thickness of the intermediate layer.
According to the Experiment 22, as shown in table 2, a laminated body was obtained according to the same procedure as the Experiment 20, except that the first structural body was made of the ceramic material of the Experiment 6, the second structural body was made of aluminum nitride and the laminated sintering was performed without the intermediate layer in N2 atmosphere. According to the Experiment 23, as shown in table 2, a laminated body was obtained according to the same procedure as the Experiment 20, except that the first structural body was made of the ceramic material of the Experiment 6, the second structural body was made of yttrium oxide and the laminated sintering was performed without the intermediate layer in N2 atmosphere. According to the Experiment 24, as shown in table 2, a laminated body was obtained according to the same procedure as the Experiment 20, except that the first structural body was made of the ceramic material of the Experiment 13, the second structural body was made of aluminum nitride AlN[1] and the laminated sintering was performed without the intermediate layer in N2 atmosphere. In all of the Experiments 22 to 24, cracks and fractures were not found at the interfaces between the layers. Further, according to each of the Experiments 22 to 24, the difference of the linear thermal expansion coefficients of the first and second structural bodies was as low as 0.3 ppm/K or lower, so that it was possible to prevent the generation of cracks and fractures without providing the intermediate layer. Besides, according to the Experiments 22 to 24, it may be provided the intermediate layer as the Experiments 20, 20-1, 21 and 21-1.
According to the Experiment 25, as shown in table 2, a laminated body was obtained according to the same procedure as the Experiment 20, except that the first structural body was composed of alumina, the second structural body was composed of aluminum nitride (AlN[1]), and the laminated sintering was performed in N2 atmosphere. According to the Experiment 26, as shown in table 2, a laminated body was obtained according to the same procedure as the Experiment 20, except that the first structural body was composed of spinel, the second structural body was composed of aluminum nitride (AlN[1]), and the laminated sintering was performed in N2 atmosphere. According to each of the Experiments 25 and 26, cracks were generated at the interface between the layers. This is because the difference between the thermal expansion coefficients of the first and second structural bodies is too large so that it could not prevent the crack formation due to the difference of thermal expansion in spite of providing the intermediate layer.
It will be described a method of producing a ceramic heater according to an embodiment of the present invention, referring to
(a) First, it was prepared materials of a susceptor (plate) (S101). As to material of the surface corrosion resistant layer 14, specifically, raw materials of MgO, Al2O3 and AlN were weighed, and wet-mixed using isopropyl alcohol as a solvent, a nylon pot, and alumina agitating media with a diameter of 5 mm for 4 hours. The mixing is performed using, for example, a large scale ball mill with its container itself rotated, which is called trommel. After the mixing, the slurry was collected and dried in nitrogen flow at 110° C. It was then passed through a sieve of 30 mesh to produce formulated powder. Besides, a molar ratio of Mg/Al in the formulated powder was 1.2.
On the other hand, as to material of the plate shaped main body 13, aluminum nitride ceramic powder was mixed with a binder for molding. The time period of mixing by trammel was about 30 minutes, for example. Thereafter, granulation was performed by means of a granulating system such as a spray drier (SD) to obtain granulated powder.
(b) Then, the formulated powder for the surface corrosion resistant layer was molded by a mechanical press under uniaxial pressure, and the granulated powder for the plate shaped main body was then added thereto and molded by the same mechanical press under uniaxial pressure to produce a preliminary molded body (S102). Then, a heat generator 4 and electrical supply terminal part 6 were embedded inside of the preliminary molded body, which was then molded by the mechanical press again.
(c) The laminated molded body produced as described above was contained in a sintering furnace such as of hot press molding and then sintered (S103). According to hot press molding, raw material powder or molded body is filled or inserted in a carbon jig and then sintered at uniaxial pressure of 30 to 50 MPa. This is suitable for sintering of ceramic materials which are difficult to density by conventional sintering at ambient pressure. The sintering conditions are under sintering temperature of 1600 to 2000° C., a pressure of 100 to 300 kgf/cm2 and sintering time period of 2 to 5 hours.
(d) On the other hand, the supporting part (shaft part) 3 is produced separately from the plate. First, materials of the shaft are prepared (S104). Specifically, formulated powder is prepared according to the same procedure as that of the plate shaped main body (S101). The thus prepared formulated powder was contained in a sintering furnace such as a cold isostatic press (CIP) and sintered to produce a molded body (S105). CIP is a method of subjecting an uniaxial molded body obtained by metal mold method to isostatic press molding so as to improve the density of and to prevent the ununiformity of the molded body. It is possible to directly fill the raw materials in a rubber mold without performing the molding using a metal mold and to perform CIP processing to obtain a molded body. The thus obtained molded body of shaft is sintered in an ambient pressure sintering furnace or the like (S106). The sintering conditions include a sintering temperature of 1600 to 2000° C., a pressure of 1 to 30 kg/cm2 and a sintering time period of 1 to 5 hours. Then, the shaft is processed in its outer periphery or by lapping (S107).
(e) The susceptor and shaft obtained according to the procedure as described above are bonded with each other in a sintering furnace by direct bonding process (S108). The sintering conditions include a sintering temperature of 1400 to 2000° C., a pressure of 100 to 300 kg/cm2 and a sintering time period of 2 to 5 hours. A ceramic heater after the bonding is subjected to processing of its side face and connection of terminals in a bonding furnace. Thereafter, washing treatment and evaluation of temperature uniformity are performed.
Besides, materials forming the surface corrosion resistant layers in the Experiments 3, 4, 5 and 6 in table 3 are that of the Experiment No. 10 in the above Example (table 1).
As comparative example 1 (Experiment No. 1), the susceptor 2 and supporting part 3 were formed from aluminum nitride powder (purity of 99.5 percent) with 5 weight percent of yttrium oxide added and bonded with each other to produce a heating apparatus.
As comparative example 2 (Experiment No. 2), the susceptor was formed of the material forming the surface corrosion resistant layer in the Experiment Nos. 3, 4, 5 and 8 in table 3. The material is that used in the Example 12 in the example section (table 1). The supporting part 3 was made from aluminum nitride powder (purity of 99.5 percent) containing 5 weight percent of yttria.
Corrosion resistance test: ICP: 800 W, Bias: 450 W, Supplied gas: NF3/O2/Ar=75/35/100 sccm, 0.05 Torr, Exposed time period: 100 hours, Temperature of sample 600° C.
Evaluated properties: Temperature uniformity on a wafer, amount of particles and surface roughness before and after the corrosion resistance test described above.
The ceramic heaters of the examples were set in a vacuum chamber, and a black body wafer for temperature measurement was set on the ceramic heater, which was heated at 550° C. Temperature distribution on the black body wafer at the temperature was measured from the outside of the chamber by infrared ray radiation thermometer (IR camera). Based on the thus obtained temperature distribution, a difference “ΔT” between the maximum and minimum temperatures was calculated. Besides, the heating of the heater at the temperature was controlled by a thermocouple not shown fitted to a back face of the ceramic susceptor.
The ceramic heaters of the examples were set in a vacuum chamber and an Si wafer was set on the ceramic heater, which was heated at 550° C. It was measured the amount of particles on a surface of the Si wafer on the side of the mounting face of the ceramic heater after the heating by a particle counter. Besides, the heating of the heater at the temperature was controlled by a thermocouple not shown fitted to a back face of the ceramic plate.
The roughness of the product surface was measured by Tailor-Hobson roughness measuring instrument. The measurement was performed at two optional positions in inside and outside parts of the plane.
According to the Experiment No. 1, although the temperature uniformity on wafer after the corrosion resistant test was good, particles were increased and the surface roughness was deteriorated to result in deterioration of temperature uniformity on wafer after the corrosion resistance test. According to the Experiment No. 2, it was extremely superior in that the temperature uniformity on wafer was not deteriorated even after the corrosion resistance test. According to Experiment Nos. 8 to 6, the temperature uniformity on wafer after the corrosion resistance test was not deteriorated, as well as the initial temperature uniformity on wafer before the corrosion resistance test was proved to be superior than that in the Experiment No. 2.
These actions and effects are epoch-making in the field of semiconductor treating system, and it can be understood that various applications are expected in the industries.
Although specific embodiments of the present invention have been described above, the invention is not to be limited to these specific embodiments and can be performed with various changes and modifications, without departing from claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2010-239000 | Oct 2010 | JP | national |
| 2011-135312 | Jun 2011 | JP | national |
| PCT/JP2011/069479 | Aug 2011 | JP | national |
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/JP2011/073770 | Oct 2011 | US |
| Child | 13864559 | US |
