1. Field of the Invention
Embodiments of the present invention generally relate to a physical vapor deposition (PVD) system and methods for depositing transparent conductive oxides (TCO) onto large area substrates by reactive sputtering.
2. Description of the Related Art
PVD using a magnetron is one method of depositing material onto a substrate. During a PVD process a target may be electrically biased so that ions generated in a process region can bombard the target surface with sufficient energy to dislodge atoms from the target. The process of biasing a target to cause the generation of a plasma that causes ions to bombard and remove atoms from the target surface is commonly called sputtering. The sputtered atoms travel generally toward the substrate being sputter coated, and the sputtered atoms are deposited on the substrate. Alternatively, the atoms react with a gas in the plasma, for example, oxygen or nitrogen, to reactively deposit a compound on the substrate.
Direct current (DC) sputtering and alternating current (AC) sputtering are forms of sputtering in which the target is biased to attract ions towards the target. The target may be biased to a negative bias in the range of about −100 to −600 V to attract positive ions of the working gas (e.g., argon) toward the target to sputter the atoms. The sides of the sputter chamber may be covered with a shield to protect the chamber walls from sputter deposition. The shield may be electrically grounded and thus provide an anode in opposition to the target cathode to capacitively couple the target power to the plasma generated in the sputter chamber.
During sputtering, material may sputter and deposit on the exposed surfaces within the chamber. When the temperature fluxuates from a processing temperature to a lower, non-processing temperature, material that has deposited on the exposed surfaces of the chamber may flake off and contaminate the substrate.
When depositing thin films over large area substrates such as glass substrates, flat panel display substrates, solar cell panel substrates, and other suitable substrates, uniform deposition on the substrate may be difficult. Therefore, there is a need in the art to reduce flaking in PVD chambers, while also uniformly depositing onto a substrate.
The present invention generally comprises one or more cooled anodes shadowing one or more gas introduction tubes where both the cooled anodes and the gas introduction tubes span a processing space defined between one or more sputtering targets and one or more substrates within a sputtering chamber. The gas introduction tubes may have gas outlets that direct the gas introduced away from the one or more substrates. The gas introduction tubes may introduce reactive gas, such as oxygen, into the sputtering chamber for depositing TCO films by reactive sputtering. During a multiple step sputtering process, the gas flows (i.e., the amount of gas and the type of gas), the spacing between the target and the substrate, and the DC power may be changed to achieve a desired result.
In one embodiment, a physical vapor deposition apparatus is disclosed. The apparatus comprises one or more sputtering targets, a substrate support, one or more anodes disposed between the one or more sputtering targets and the substrate support, and one or more gas distribution tubes coupled with the one or more anodes and one or more gas sources.
In another embodiment, a physical vapor deposition apparatus is disclosed. The apparatus comprises a chamber body, one or more sputtering targets disposed within the chamber body, a substrate support disposed within the chamber body, and one or more tubes disposed within the chamber body between the one or more sputtering targets and the substrate support, the one or more tubes comprising an anode and one or more gas outlets.
In yet another embodiment, a physical vapor deposition method is disclosed. The method comprises positioning at least one tube assembly in a processing space between one or more sputtering targets and a susceptor, the tube assembly comprising an anode with a cooling channel therein and a gas distribution tube, cooling the at least one tube assembly with a cooling fluid flowing within the anode, flowing processing gas through the gas distribution tube, and sputtering material from the one or more sputtering targets onto a substrate.
So that the manner in which the above recited features of the present invention can be understood in detail, a more particular description of the invention, briefly summarized above, may be had by reference to embodiments, some of which are illustrated in the appended drawings. It is to be noted, however, that the appended drawings illustrate only typical embodiments of this invention and are therefore not to be considered limiting of its scope, for the invention may admit to other equally effective embodiments.
To facilitate understanding, identical reference numerals have been used, where possible, to designate identical elements that are common to the figures. It is contemplated that elements disclosed in one embodiment may be beneficially utilized on other embodiments without specific recitation.
The present invention generally comprises one or more cooled anodes shadowing one or more gas introduction tubes where both the cooled anodes and the gas introduction tubes span a processing space defined between one or more sputtering targets and one or more substrates within a sputtering chamber. The gas introduction tubes may have gas outlets that direct the gas introduced away from the one or more substrates. The gas introduction tubes may introduce reactive gas, such as oxygen, into the sputtering chamber for depositing TCO films by reactive sputtering. During a multiple step sputtering process, the gas flows (i.e., the amount of gas and the type of gas), the spacing between the target and the substrate, and the DC power may be changed to achieve a desired result.
The invention is illustratively described and may be used in a PVD chamber for processing large area substrates, such as a 4300 PVD chamber, available from AKT®, a subsidiary of Applied Materials, Inc., Santa Clara, Calif. However, it should be understood that the sputtering target may have utility in other system configurations, including those systems configured to process large area round substrates and those systems produced by other manufacturers.
The target 104 may comprise one or more targets 104. In one embodiment, the target 104 may comprise a large area sputtering target 104. In another embodiment, the target 104 may comprise a plurality of tiles. In yet another embodiment, the target 104 may comprise a plurality of target strips. In still another embodiment, the target may comprise one or more cylindrical, rotary targets. The target 104 may be bonded to a backing plate 116 by a bonding layer 134. To control the temperature of the target 104, cooling channels 136 may be present in the backing plate 116. One or more magnetrons 118 may be disposed behind the backing plate 116. The magnetrons 118 may scan across the backing plate 116 in a linear movement or in a two dimensional path. The walls of the chamber may be shielded from deposition by a dark space shield 120 and a chamber shield 122.
The grounded chamber walls may function as an anode and attract electrons from the plasma and hence, may tend to create a higher density of plasma near the chamber walls. A higher density of plasma near the chamber walls may increase the deposition on the substrate near the chamber walls and decrease the deposition away from the chamber walls. The grounded susceptor 106, on the other hand, also functions as an anode. For large area substrate deposition, the susceptor 106 may span a significant length of the processing space 158. Thus, the susceptor 106 may provide a path to ground for electrons not only at the edge of the susceptor 106, but also at the middle of the susceptor 106. The path to ground at the middle of the susceptor 106 balances out the path to ground at the edge of the susceptor 106 and the chamber walls because each anode, be it the chamber walls or the susceptor 106, will equally function as an anode and uniformly spread the plasma across the processing space. By uniformly distributing the plasma across the processing space, uniform deposition across the substrate 102 may occur.
When the substrate 102 is an insulating substrate (such as glass or polymer), the substrate 102 is non-conductive and thus electrons may not follow through the substrate 102. As a consequence, when the substrate 102 substantially covers the susceptor 106, the susceptor 106 may not provide sufficient anode surfaces.
For large area substrates 102, such as solar cell panels or substrates 102 for flat panel displays, the size of the substrate 102 blocking the path to ground through the susceptor 106 may be significant. Substrates 102 as large as 1 meter by 1 meter are not uncommon in the flat panel display industry. For a 1 meter by 1 meter substrate 102, a path to ground through the susceptor 106 may be blocked for an area of 1 square meter. Therefore, the chamber walls and the edges of the susceptor 106 that are not covered by the substrate are the only paths to ground for the electrons in the plasma. No path to ground exists near the center of the substrate 102. With a large area substrate 102, a high density plasma may form near the chamber walls and the edge of the susceptor 106 that are not covered by the substrate 102. The high density plasma near the chamber walls and the susceptor 106 edge may thin the plasma near the center of the processing region where no path to ground exists. Without a path to ground near the center of the processing area, the plasma may not be uniform and hence, the deposition on the large area substrate may not be uniform.
To help provide uniform sputtering deposition across a substrate 102, an anode 124 may be placed between the target 104 and the substrate 102. In one embodiment, the anode 124 may be bead blasted stainless steel coated with arc sprayed aluminum. In one embodiment, one end of the anode 124 may be mounted to the chamber wall by a bracket 130. As shown in
The anode 124 provides a charge in opposition to the target 104 so that charged ions will be attracted thereto rather than to the chamber walls which are typically at ground potential. By providing the anode 124 between the target 104 and the substrate 102, the plasma may be more uniform, which may aid in the deposition.
During processing, the temperatures in the chamber 100 may increase up to about 400 degrees Celsius. Between processing (i.e., when substrates 102 are removed from and inserted into the chamber 100), the temperature of the chamber 100 may be reduced to about room temperature (i.e., about 25 degrees Celsius). The temperature change may cause the anodes 124 to expand and contract. During processing, material from the target 104 may deposit onto the anode 124 because the anode 124 lies between the target 104 and the substrate 102. The material deposited onto the anode 124 may flake off due to expansion and contraction.
Flowing a cooling fluid through the one or more anodes 124 may control the temperature of the anodes 124 and thus reduce any expansion and contraction of the anodes 124. By reducing the amount of expansion and contraction of the anodes 124, flaking of material from the anodes 124 may be reduced.
For reactive sputtering, it may be beneficial to provide a reactive gas into the chamber 100. One or more gas introduction tubes 126 may also span the distance across the chamber 100 between the target 104 and the substrate 102. The gas introduction tubes 126 may introduce sputtering gases such as inert gases including argon as well as reactive gases such as oxygen, nitrogen, etc. The gases may be provided to the gas introduction tubes 126 from a gas panel 132 that may introduce one or more gases such as argon, oxygen, and nitrogen.
The gas introduction tubes 126 may be disposed between the substrate 102 and the target 104 at a location below the one or more anodes 124. The gas outlets 138 on the gas distribution tubes 126 may face away from the substrate 102 to reduce direct exposure of the substrate 102 to processing gas. The gas introduction tubes 126 may have a diameter B about ten times greater than the diameter of the gas outlets 138 so that the flow of gas through each gas outlet 138 may be substantially equal. The anodes 124 may shield the gas introduction tubes 126 from deposition during processing. Shielding the gas introduction tubes 126 with the anodes 124 may reduce the amount of deposition that may cover the gas outlets 138 and clog the gas outlets 138. The anodes 124 may have a larger diameter as shown by arrows B than the diameter of the gas introduction tubes 126 as shown by arrows C. The gas introduction tubes 126 may be coupled with the anodes 124 by one or more couplers 128.
During processing, the gas introduction tubes 126 may be subjected to the same temperature fluxuations as the anodes 124. Therefore, it may be beneficial to cool the gas introduction tubes 126 as well. The coupling 128 may thus be made of thermally conductive material to permit the gas introduction tubes 126 to be conductively cooled. Additionally, the coupling 128 may be electrically conductive as well so that the gas introduction tubes 126 are grounded and function as anodes. In one embodiment, the coupling 128 may comprise metal. In another embodiment, the coupling 128 may comprise stainless steel.
Reactive sputtering may be used to deposit a TCO layer onto a substrate for such applications as solar panels and thin film transistors. TCO layers may be disposed within a solar panel between a reflector layer and a p-i-n structure, between adjacent p-i-n structures, and between glass and a p-i-n structure.
The TCO layers 804, 812, 854, 862, 870 may be deposited by reactive sputtering to a thickness of about 250 Angstroms to about 10,000 Angstroms and may comprise one or more elements selected from the group consisting of In, Sn, Zn, Cd, and Ga. One or more dopants may also be present in the TCO. Exemplary dopants include Sn, Ga, Ca, Si, Ti, Cu, Ge, In, Ni, Mn, Cr, V, Mg, SixNy, AlxOy, and SiC. Exemplary compounds that may constitute the TCO layers include binary compounds such as In2O3, SnO2, ZnO, and CdO; ternary compounds such as In4SnO12, ZnSnO3, and Zn2In2O5; binary-binary compounds such as ZnO—SnO2, and ZnO—In2O3—SnO2; and doped compounds such as In2O3:Sn (ITO), SnO2:F, ZnO:In (IZO), ZnO:Ga, ZnO:Al (AZO), ZnO:B, and ZnSnO3:In.
The TCO layers 804, 812, 854, 862, 870 may be formed by reactive sputtering using a PVD chamber as described above. The sputtering target may comprise the metal of the TCO. Additionally, one or more dopants may be present in the sputtering target. For example, for an AZO TCO layer, the sputtering target may comprise zinc and some aluminum as a dopant. The aluminum dopant in the target may comprise about 2 atomic percent to about 6 atomic percent of the target. By reactively sputtering the TCO, resistivities of less than 5×10−4 ohm-cm have been achieved. In one embodiment, the resistivity is 3.1×10−4 ohm-cm. The TCO may have a haze of less than about 1 percent. In one embodiment, the haze may more than 10 percent.
Various sputtering gases may be supplied to the PVD chamber during the sputtering process to reactively sputter the TCO. Sputtering gases that may be supplied include inert gases, oxygen containing gases, non-oxygen containing additives, and combinations thereof. The flow rates for the gases may be proportional to the chamber volume. Exemplary inert gases that may be used include Ar, He, Ne, Xe, and combinations thereof may be provided at a flow rate of about 100 sccm to about 200 sccm. Exemplary oxygen containing gases that may be used include CO, CO2, NO, N2O, H2O, O2, CxHyOz, and combinations thereof. The oxygen containing gases may be supplied at a flow rate of about 5 sccm to about 500 sccm. In one embodiment, the oxygen containing gases may be supplied at a flow rate of about 10 sccm to about 30 sccm. Exemplary non-oxygen additive gases that may be used include N2, H2, CxHy, NH3, NF3, SiH4, B2H6, PH3, and combinations thereof. The non-oxygen additive gases may be supplied at a flow rate of about 100 sccm or more. In one embodiment, the non-oxygen additive gases may be supplied at a flow rate of about 200 sccm or more.
To reactively sputter the TCO, DC power may be supplied. In one embodiment, the DC power may be pulsed with a frequency up to about 50 kHz. The duty cycle of the pulsed power may also be adjusted. The temperature of the substrate during sputtering may range from about room temperature to about 450 degrees Celsius. In one embodiment, the substrate temperature may be about 25 degrees Celsius. The spacing between the target and the substrate may be about 17 mm to about 85 mm.
The reactive sputtering of the TCO may occur in multiple steps. By multiple steps it is to be understood to include separate, independent steps as well as a continuous process where one or more deposition parameters change. The power supplied may change during the deposition, the flow rate of the sputtering gases may change during the deposition, the temperature may change during deposition, and the spacing between the target and the substrate may change during the deposition. The changing may occur during a deposition step or between deposition steps. When depositing the TCO, the initial portion of the layer may comprise more metal than oxide because the metal may provide good contact with a layer upon which it is deposited. As the TCO layer gets thicker, more oxygen may be desired in the layer up to the point of complete oxidation. By adjusting the parameters during deposition, the film properties of the TCO, such as a band gap, stress, and refractive index, may be adjusted.
While the foregoing is directed to embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
This application is a continuation of co-pending U.S. patent application Ser. No. 11/697,476 (APPM/10586.P1), filed Apr. 6, 2007, which application is a continuation-in-part of U.S. patent application Ser. No. 11/399,233 (APPM/10586), filed Apr. 6, 2006. U.S. patent application Ser. No. 11/697,476 (APPM/10586.P1), filed Apr. 6, 2007 also claims the benefit of U.S. Provisional Patent Application Ser. No. 60/807,391 (APPM/11277L), filed Jul. 14, 2006. Each of the aforementioned related patent applications is herein incorporated by reference.
Number | Date | Country | |
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60807391 | Jul 2006 | US |
Number | Date | Country | |
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Parent | 11697476 | Apr 2007 | US |
Child | 13231182 | US |
Number | Date | Country | |
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Parent | 11399233 | Apr 2006 | US |
Child | 11697476 | US |