Disclosed embodiments relate to the field of material vapor transport deposition (VTD) methods and systems, and more particularly to a material vapor transport deposition method and system which permits a controlled co-deposition of different materials.
Photovoltaic devices such as photovoltaic modules or cells, can include semiconductor and other materials deposited over a substrate using various deposition systems and techniques. One example is the deposition of a semiconductor material such as cadmium sulfide (CdS) or cadmium telluride (CdTe) thin films over a substrate using a VTD system. A VTD system may use a powder delivery unit, a powder vaporizer and vapor distributor, and a vacuum deposition unit.
VTD powder vaporizers are designed to vaporize or sublimate raw material powder into a gaseous form. In conventional powder vaporizers, raw material powder combined with a carrier gas is injected into a permeable heated cylinder from a powder delivery unit. The material is vaporized in the cylinders and the vaporized material diffuses through the permeable walls of the vaporizer into the distributor. The distributor collects and directs the flow of vaporized raw material for deposition as a thin film layer on a substrate. The distributor typically surrounds the vaporizer cylinder and directs collected vapors towards openings which face towards a substrate.
It may be desirable for certain deposition methods to introduce a dopant into the semiconductor material which can react with semiconductor material and form a vapor phase compound within vaporizer 12 during the deposition process. For example, CdTe semiconductor material powder and Si dopant powder can be combined as a Si—CdTe powder mixture with a predetermined blending concentration and loaded into powder feeders 21 and 23. The Si—CdTe powder mixture is then introduced into vaporizer and distributor assembly 10 for chemical reaction and co-vaporization. After diffusion through vaporizer 12, the mixture of vapors is captured in the vapor housing 15 and directed through holes 14 for deposition as a thin film layer on substrate 13. The vaporization of the Si—CdTe powder mixture does not allow for composition control of the predetermined blending concentration of the Si—CdTe powder mixture unless the vapor transport deposition system 20 is stopped, the dopant/semiconductor powder mixture is removed from powder feeders 21 and 23 and an alternate dopant/semiconductor powder mixture is loaded. This complete shut-down of the VTD system for adjustment in the blending concentration of the dopant/semiconductor powder mixture is time consuming and costly.
An improved vapor transport deposition system which mitigates against the noted problems is desirable.
In the following detailed description, reference is made to the accompanying drawings which form a part hereof, and which illustrate specific embodiments of the invention. These embodiments are described in sufficient detail to enable those of ordinary skill in the art to make and use them. It is also understood that structural, logical, or procedural changes may be made to the specific embodiments disclosed herein without departing from the spirit or scope of the invention.
According to one example embodiment, an improved vapor transport deposition method and system are provided which include a distributor coupled to two vaporizers. The distributor may employ a thermal conductive material and be heated by radiant heat from the two vaporizers. Each respective vaporizer can independently vaporize or sublimate a different raw material powder into a respective raw material vapor and the two vapors may diffuse out of the respective vaporizers into a common chamber within the distributor. The two raw material vapors combine within the distributor chamber and the combined vapor is directed out of the distributor chamber for deposition on a substrate as a thin film layer composed of multiple materials. This example embodiment may further include at least two powder feeders for providing at least two different vaporizable powders to the respective vaporizers. A first powder feeder may be loaded with a first vaporizable material and a second powder feeder may be loaded with a different second vaporizable material. At least two carrier gas sources may provide a carrier gas, for example Helium (He), into respective powder feeders to transport the respective vaporizable material powders from the powder feeders into the respective vaporizers.
The concentration balance of the compounds in the combined vapor may be determined and altered by adjusting the flow of vapor from one and/or both of the respective vaporizers into the distributor. Flow of the vapor into the respective distributor is controlled by adjusting material flow rates at other points in the VTD system. For example, vapor flow may be controlled by adjusting vibration speed and amplitude of the powder feeders that process the raw material into a powder form. The flow of vapor may also be controlled by adjusting the flow rate of the carrier gas, for example Helium gas, that transports the raw material from the respective powder feeders into the respective vaporizers. These adjustments control raw material flow into the vaporizer, and correspondingly control the flow of vapor from the respective vaporizer into the common distributor chamber. Therefore, the relative amount of raw material from the respective vaporizer in the vapor mixture can be controlled to alter the ultimate thin film layer composition. This independent control of the raw material vapor from the respective vaporizer into the distributor allows for easy control of the composition of the combination vapor without a shut-down of the vapor transport deposition system.
This improved vapor transport deposition method and system can be used to deposit a single vaporizable material that is loaded into both vaporizers. For deposition of a single vaporizable material, independent control of the raw material vapor from multiple vaporizers allows for system redundancy. A single vaporizer can continue to operate if components of the second vaporizer malfunction and must be repaired. This maintains continual production during repair or component replacement.
This improved vapor transport deposition method and system can also be used to co-deposit any two or more vaporizable materials or combinations of vaporizable materials. For example, the various vaporizable materials may include but are not limited to combinations of multiple semiconductor materials, semiconductor alloys, a semiconductor material and a dopant, or multiple semiconductor materials and/or dopant. Vaporizable semiconductor materials may, for example, include copper indium gallium selenide (CIGS) or a transition metal (Group 12) combined with a chalcogenide (Group 18) such as cadmium telluride (CdTe), cadmium sulfide (CdS), zinc telluride (ZnTe) or zinc sulfide (ZnS). Suitable vaporizable dopants may include Si, CuCl2 or MnCl2. Suitable semiconductor alloys may include CdxZn1−xTe, CdTexS1−x, or phase change material such as GeSbTe.
In one exemplary use of the embodiment described above, cadmium telluride (CdTe) is co-deposited with a Si dopant as a semiconductor thin layer. A first powder feeder may be loaded with cadmium telluride (CdTe) and a second powder feeder may be loaded with a concentrated Si:CdTe powder mix as a dopant. The CdTe semiconductor material powder and the concentrated Si:CdTe dopant powder are delivered by the respective powder feeders to the respective vaporizers. The CdTe material is vaporized to form Cd(g) and Te(g) and the concentrated Si:CdTe dopant mixture reacts and is vaporized to form SiTex(g), Cd(g) and Te(g). The Cd(g), Te(g) and SiTex(g) diffuse through the respective vaporizers and combine in the common distributor chamber to form a mixture of all three gasses, which is directed out of the distributor for co-deposition as a thin film layer on a substrate. In this example, independent control of the vapor flow from the respective vaporizers allows for composition control of the mixture of Cd(g), Te(g) and Si(g) to ensure optimal production of SiTeX (gas) without the need for time consuming and costly VTD system shut-downs to adjust powder composition balance.
In another example use of the embodiment described above, cadmium telluride (CdTe) is co-deposited with zinc telluride (ZnTe) to form a semiconductor alloy thin layer. A first powder feeder may be loaded with cadmium telluride (CdTe) and a second powder feeder may be loaded with zinc telluride (ZnTe). The CdTe semiconductor material powder and the ZnTe semiconductor material powder are delivered by the respective powder feeders to the respective vaporizers. The CdTe material is vaporized to form Cd(g) and Te(g) and the ZnTe material is vaporized to form Zn(g) and Te(g). The Cd(g), Te(g) and Zn(g) diffuse through the respective vaporizers and combine in the common distributor chamber to form a mixture of gasses. The mixture of gasses is directed out of the distributor for deposition as a CdxZn1−xTe thin film alloy layer on a substrate. Independent control of the vapor flow from the respective vaporizers allows for composition control of the mixture of Cd(g), Te(g) and Zn(g) to ensure optimal composition of the CdxZn1−xTe thin film alloy layer without excess reactants.
Material feeders 43a, 43b and 44a, 44b may be any type of material supplier that can be utilized for processing the raw material into a powder form and feeding the material powder into the vaporizer and distributor assembly 30, for example, vibratory powder feeders, fluidized bed feeders and rotary disk feeders that are commercially available. As described above, the vibration speed and/or amplitude used to process the raw material into the powder form can control flow of raw material from material feeders 43a, 43b and 44a, 44b through respective vaporization units 40a, 40b and to the vaporizer and distributor assembly 30. The vibration speed and/or amplitude of the material feeders 43a, 43b and 44a, 44b may be adjusted by a manual input or a digital/analog signal.
The inert carrier gases input from inert carrier gas sources 45a, 46a, and 45b, 46b can alternatively be another inert gas such as nitrogen, neon, argon or krypton, or combinations of these gases. It is also possible for the carrier gas to be mixed with and include some amount of a reactive gas such as oxygen that can advantageously affect growth properties of the material. A flow rate of about 0.0001 to about 10 slpm of the carrier gas has been determined to be sufficient to facilitate flow of the powder out of material feeders 43a, 43b and 44a, 44b, through vaporization units 40a, 40b and through the vaporizer and distributor assembly 30. Mass flow controllers 47a, 47b, 48a, 48b may adjust flow rate between about 0.0001 to about 10 slpm during the deposition process to control substrate composition.
The vaporizer units 40a, 40b are made of any permeable material that is preferably electrically conductive, such as silicon carbide, and heated by electric power 29 to provide for vaporization or sublimation of material. Furthermore, the vapor housings 15a, 15b are generally a tubular shape that encloses the vaporizer units 40a, 40b as illustrated in
The distributor unit 50 is heated by radiant heat from vaporizers 40a and 40b, which can be powered by electricity. Vaporizers 40a and 40b provide radiant heat to the surface of distributor unit 50 sufficient to maintain a temperature up to about 1350° C. in the distributor chamber 57. Vapor pressure within distributor chamber 57 is between about 1 to about 10 Torr.
The single opening 60 or the plurality of openings 60 for directing the combination material vapor out of the distributor chamber 57 are preferably constructed as slit-shaped or circular openings, which can have a uniform width, as more clearly shown in
A method 100 for depositing multiple materials in combination as a layer on a substrate using a VTD system with a vaporizer and distributor assembly as described herein, is shown in
The steps 109 and 110 of using the respective vaporizer units to vaporize the respective material powders into respective material vapors are further outlined in
The steps 111 and 112 of passing the respective material vapors from the respective vaporizers into the distributor unit are further outline in
The step 114 of adjusting the composition of the combined material vapor by adjusting the flow of the respective vapors from the respective vaporizer units into the distributor unit is further outlined in
The system illustrated in
It should be noted that since the deposition system illustrated in
While embodiments have been described in detail, it should be readily understood that the invention is not limited to the disclosed embodiments. Rather the embodiments can be modified to incorporate any number of variations, alterations, substitutions, or equivalent arrangements not heretofore described without departing from the spirit and scope of the invention.
Number | Date | Country | |
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61543627 | Oct 2011 | US |