Field
The field relates generally to manifolds for uniform vapor deposition, and, in particular, to manifolds for improving reactant mixing in atomic layer deposition (ALD) reactors.
Description of the Related Art
There are several vapor deposition methods for depositing thin films on surfaces of substrates. These methods include vacuum evaporation deposition, Molecular Beam Epitaxy (MBE), different variants of Chemical Vapor Deposition (CVD) (including low-pressure and organometallic CVD and plasma-enhanced CVD), and Atomic Layer Deposition (ALD).
In an ALD process, one or more substrates with at least one surface to be coated are introduced into a deposition chamber. The substrate is heated to a desired temperature, typically above the condensation temperatures of the selected vapor phase reactants and below their thermal decomposition temperatures. One reactant is capable of reacting with the adsorbed species of a prior reactant to form a desired product on the substrate surface. Two, three or more reactants are provided to the substrate, typically in spatially and temporally separated pulses.
In an example, in a first pulse, a first reactant representing a precursor material is adsorbed largely intact in a self-limiting process on a wafer. The process is self-limiting because the vapor phase precursor cannot react with or adsorb upon the adsorbed portion of the precursor. After any remaining first reactant is removed from the wafer or chamber, the adsorbed precursor material on the substrate reacted with a subsequent reactant pulse to form no more than a single molecular layer of the desired material. The subsequent reactant may, e.g., strip ligands from the adsorbed precursor material to make the surface reactive again, replace ligands and leave additional material for a compound, etc. In an unadulterated ALD process, less than a monolayer is formed per cycle on average due to steric hindrance, whereby the size of the precursor molecules prevent access to adsorption sites on the substrate, which may become available in subsequent cycles. Thicker films are produced through repeated growth cycles until the target thickness is achieved. Growth rate is often provided in terms of angstroms per cycle because in theory the growth depends solely on number of cycles, and has no dependence upon mass supplied or temperature, as long as each pulse is saturative and the temperature is within the ideal ALD temperature window for those reactants (no thermal decomposition and no condensation).
Reactants and temperatures are typically selected to avoid both condensation and thermal decomposition of the reactants during the process, such that chemical reaction is responsible for growth through multiple cycles. However, in certain variations on ALD processing, conditions can be selected to vary growth rates per cycle, possibly beyond one molecular monolayer per cycle, by utilizing hybrid CVD and ALD reaction mechanisms. Other variations maybe allow some amount of spatial and/or temporal overlap between the reactants. In ALD and variations thereof, two, three, four or more reactants can be supplied in sequence in a single cycle, and the content of each cycle can be varied to tailor composition.
During a typical ALD process, the reactant pulses, all of which are in vapor form, are pulsed sequentially into a reaction space (e.g., reaction chamber) with removal steps between reactant pulses to avoid direct interaction between reactants in the vapor phase. For example, inert gas pulses or “purge” pulses can be provided between the pulses of reactants. The inert gas purges the chamber of one reactant pulse before the next reactant pulse to avoid gas phase mixing. To obtain a self-limiting growth, a sufficient amount of each precursor is provided to saturate the substrate. As the growth rate in each cycle of a true ALD process is self-limiting, the rate of growth is proportional to the repetition rate of the reaction sequences rather than to the flux of reactant.
The systems and methods of the present invention have several features, no single one of which is solely responsible for its desirable attributes. Without limiting the scope of this invention as expressed by the claims which follow, various features will now be discussed briefly. After considering this discussion, and particularly after reading the section entitled “Detailed Description,” one will understand how the features described herein provide several advantages over traditional gas delivery methods and systems.
In one embodiment, a semiconductor processing device is disclosed. The semiconductor processing device can include a manifold comprising a bore and having an inner wall, the inner wall at least partially defining the bore. A first axial portion of the bore can extend along a longitudinal axis of the manifold. The semiconductor processing device can include a supply channel that provides fluid communication between a gas source and the bore. The supply channel can comprise a slit defining an at least partially annular gap through the inner wall of the manifold to deliver a gas from the gas source to the bore. The at least partially annular gap can be revolved about the longitudinal axis.
In another embodiment, a semiconductor processing device is disclosed. The semiconductor processing device can include a manifold comprising a bore and a supply channel that provides fluid communication between a gas source and the bore to supply a gas to the bore. The bore can comprise a channel having an annular flow portion with an at least partially annular cross-section and a non-annular flow portion with a non-annular cross-section, the non-annular flow portion disposed downstream of the annular flow portion.
In another embodiment, a method of deposition is disclosed. The method can include supplying a gas through a supply channel to a bore of a manifold. The method can include creating an at least partially annular flow pattern in an annular flow portion of the bore such that the gas flows along a longitudinal axis of the manifold with an at least partially annular cross-section. Downstream of the annular flow portion, a non-annular flow pattern can be created in a non-annular portion of the bore such that the gas flows along the longitudinal axis with a non-annular cross-section.
In another embodiment, a method of deposition is disclosed. The method can include supplying a gas to a supply channel. The method can include directing the gas from the supply channel to a bore of a manifold through a slit defining an at least partially annular gap along an inner wall of the manifold, the at least partially annular gap revolved about a longitudinal axis of the manifold.
In another embodiment, a semiconductor processing device is disclosed. The semiconductor processing device can include a manifold comprising a bore therein, the bore defining a gas passageway between a first end portion of the manifold and a second end portion of the manifold. The first end portion can be disposed opposite to and spaced from the second end portion along a longitudinal axis of the manifold by a first distance. The gas passageway can extend through the manifold for a second distance larger than the first distance. A reaction chamber can be disposed downstream of and in fluid communication with the bore.
In another embodiment, a semiconductor processing device is disclosed. The semiconductor processing device can include a manifold comprising a bore having an axial portion that defines a longitudinal axis of the manifold and a lateral portion extending non-parallel to the longitudinal axis. The semiconductor processing device can include a supply channel that supplies gas to the axial portion of the bore at a first location along the longitudinal axis. The lateral portion can be disposed at a second location downstream of the first location, the lateral portion extending non-parallel relative to the longitudinal axis. The semiconductor processing device can include a reaction chamber disposed downstream of and in fluid communication with the bore.
In another embodiment, a method of deposition is disclosed. The method can include providing a manifold comprising a bore therein. The bore can define a gas passageway between a first end portion of the manifold and a second end portion of the manifold. The first end portion can be disposed opposite to and spaced from the second end portion along a longitudinal axis of the manifold by a first distance. The method can comprise supplying a reactant gas to the bore. The method can comprise directing the reactant gas along the gas passageway from the first end portion to the second end portion for a second distance, the second distance larger than the first distance.
In another embodiment, a method of deposition is disclosed. The method can include providing a manifold comprising a bore having an axial portion that defines a longitudinal axis of the manifold and a lateral portion extending non-parallel to the longitudinal axis. The method can include supplying a reactant gas to the axial portion of the bore at a first location along the longitudinal axis. The method can include directing the reactant gas through the axial portion of the bore parallel to the longitudinal axis. Downstream of the axial portion, the reactant gas can be directed through the lateral portion of the bore in a direction non-parallel to the longitudinal axis.
In another embodiment, a semiconductor processing device is disclosed. The semiconductor processing device can include a manifold comprising a bore defining an inner wall a channel through the manifold and a source of gas. A supply channel can deliver the gas to the bore by way of an opening on the inner wall of the bore. All the gas can be delivered to the bore by the opening.
In another embodiment, a method of deposition is disclosed. The method can include providing a manifold comprising a bore having an inner wall and defining a channel through the manifold. The method can include supplying all of a reactant gas through a single opening on the inner wall of the bore.
These and other features, aspects and advantages of the present invention will now be described with reference to the drawings of several embodiments, which embodiments are intended to illustrate and not to limit the invention.
In vapor or gas deposition processes, it can be important to provide uniform deposition across the width or major surface of the substrate (e.g., a semiconductor wafer). Uniform deposition ensures that deposited layers have the same thickness and/or chemical composition across the substrate, which improves the yield of integrated devices (e.g., processors, memory devices, etc.), and therefore the profitability per substrate. To improve the uniformity of deposition, various embodiments disclosed herein can enhance the mixing profile of the different gases supplied within a manifold of the semiconductor processing system. Enhanced mixing of supplied gases can beneficially supply a relatively uniform gas mixture across the major surface of the substrate.
The embodiments disclosed herein can be utilized with semiconductor processing devices configured for any suitable gas or vapor deposition process. For example, the illustrated embodiments show various systems for depositing material on a substrate using atomic layer deposition (ALD) techniques. Among vapor deposition techniques, ALD has many advantages, including high conformality at low temperatures and fine control of composition during the process. ALD type processes are based on controlled, self-limiting surface reactions of precursor chemicals. Gas phase reactions are avoided by feeding the precursors alternately and sequentially into the reaction chamber. Vapor phase reactants are separated from each other in the reaction chamber, for example, by removing excess reactants and/or reactant by-products from the reaction chamber between reactant pulses. Removal can be accomplished by a variety of techniques, including purging and/or lowering pressure between pulses. Pulses can be sequential in a continuous flow, or the reactor can be isolated and can backfilled for each pulse.
Briefly, a substrate is loaded into a reaction chamber and is heated to a suitable deposition temperature, generally at lowered pressure. Deposition temperatures are typically maintained below the precursor thermal decomposition temperature but at a high enough level to avoid condensation of reactants and to provide the activation energy for the desired surface reactions. Of course, the appropriate temperature window for any given ALD reaction will depend upon the surface termination and reactant species involved.
A first reactant is conducted into the chamber in the form of vapor phase pulse and contacted with the surface of a substrate. Conditions are preferably selected such that no more than about one monolayer of the precursor is adsorbed on the substrate surface in a self-limiting manner. Excess first reactant and reaction byproducts, if any, are purged from the reaction chamber, often with a pulse of inert gas such as nitrogen or argon.
Purging the reaction chamber means that vapor phase precursors and/or vapor phase byproducts are removed from the reaction chamber such as by evacuating the chamber with a vacuum pump and/or by replacing the gas inside the reactor with an inert gas such as argon or nitrogen. Typical purging times for a single wafer reactor are from about 0.05 to 20 seconds, more preferably between about 1 and 10 seconds, and still more preferably between about 1 and 2 seconds. However, other purge times can be utilized if desired, such as when depositing layers over extremely high aspect ratio structures or other structures with complex surface morphology is needed, or when a high volume batch reactor is employed. The appropriate pulsing times can be readily determined by the skilled artisan based on the particular circumstances.
A second gaseous reactant is pulsed into the chamber where it reacts with the first reactant bound to the surface. Excess second reactant and gaseous by-products of the surface reaction are purged out of the reaction chamber, preferably with the aid of an inert gas. The steps of pulsing and purging are repeated until a thin film of the desired thickness has been formed on the substrate, with each cycle leaving no more than a molecular monolayer. Some ALD processes can have more complex sequences with three or more precursor pulses alternated, where each precursor contributes elements to the growing film. Reactants can also be supplied in their own pulses or with precursor pulses to strip or getter adhered ligands and/or free by-product, rather than contribute elements to the film. Additionally, not all cycles need to be identical. For example, a binary film can be doped with a third element by infrequent addition of a third reactant pulse, e.g., every fifth cycle, in order to control stoichiometry of the film, and the frequency can change during the deposition in order to grade film composition. Moreover, while described as starting with an adsorbing reactant, some recipes may start with the other reactant or with a separate surface treatment, for example to ensure maximal reaction sites to initiate the ALD reactions (e.g., for certain recipes, a water pulse can provide hydroxyl groups on the substrate to enhance reactivity for certain ALD precursors).
As mentioned above, each pulse or phase of each cycle is preferably self-limiting. An excess of reactant precursors is supplied in each phase to saturate the susceptible structure surfaces. Surface saturation ensures reactant occupation of all available reactive sites (subject, for example, to physical size or steric hindrance restraints) and thus ensures excellent step coverage over any topography on the substrate. In some arrangements, the degree of self-limiting behavior can be adjusted by, e.g., allowing some overlap of reactant pulses to trade off deposition speed (by allowing some CVD-type reactions) against conformality. Ideal ALD conditions with reactants well separated in time and space provide near perfect self-limiting behavior and thus maximum conformality, but steric hindrance results in less than one molecular layer per cycle. Limited CVD reactions mixed with the self-limiting ALD reactions can raise the deposition speed. While embodiments described herein are particularly advantageous for sequentially pulsed deposition techniques, like ALD and mixed-mode ALD/CVD, the manifold can also be employed for pulsed or continuous CVD processing.
Examples of suitable reactors that may be used include commercially available ALD equipment such as any of the EmerALD® or Eagle® series reactors, available from ASM International of Almere, the Netherlands. Many other kinds of reactors capable of ALD growth of thin films, including CVD reactors equipped with appropriate equipment and means for pulsing the precursors, can be employed. In some embodiments a flow type ALD reactor is used, as compared to a backfilled reactor. In some embodiments, the manifold is upstream of an injector designed to distribute gas into the reaction space, particularly a dispersion mechanism such as a showerhead assembly above a single-wafer reaction space.
The ALD processes can optionally be carried out in a reactor or reaction space connected to a cluster tool. In a cluster tool, because each reaction space is dedicated to one type of process, the temperature of the reaction space in each module can be kept constant, which improves the throughput compared to a reactor in which is the substrate is heated to the process temperature before each run. A stand-alone reactor can be equipped with a load-lock. In that case, it is not necessary to cool down the reaction space between each run. These processes can also be carried out in a reactor designed to process multiple substrates simultaneously, e.g., a mini-batch type showerhead reactor.
The inert gas distribution channel 40 feeds inert gas to two inert gas passageways 42a, 42b, each of which can be connected to an inert gas valve. The inert gas passageways 42a, 42b connect with the inert gas distribution channel 40 at different angular locations distributed about the axis of the bore 30 (as viewed in a transverse cross-section). In the illustrated arrangement, the inert gas passageways 42a, 42b connect with the inert gas distribution channel 40 about 90° apart from one another, and about 135° (in opposite directions) from where the inert gas inlet 22 connects with the inert gas distribution channel 40.
The flow path 1 also includes a reactant gas passageway 37 which is in fluid communication with a reactant gas distribution channel 36. The reactant gas distribution channel 36 extends generally in a plane intersecting the longitudinal axis of bore 30, and is generally concentric with the inert gas distribution channel 40. The reactant gas distribution channel 36 conveys gas to multiple, e.g., three reactant gas supply channels 38a, 38b, 38c (only two of which are visible in
The flow path 1 also includes another reactant gas passageway 44b which is in fluid communication with a reactant gas distribution channel 50. The reactant gas distribution channel 50 extends generally in a plane intersecting the longitudinal axis of bore 30. The reactant gas distribution channel 50 conveys reactant gas to multiple, e.g., three reactant gas supply channels 52a, 52b, 52c (only two of which are visible in
The flow path 1 also includes a further reactant gas inlet 44a which is in fluid communication with a reactant gas distribution channel 46. The reactant gas distribution channel 46 extends generally in a plane intersecting the longitudinal axis of bore 30. The reactant gas distribution channel 46 conveys reactant gas to multiple, e.g., three reactant gas supply channels 48a, 48b, 48c, each of which connects with the reactant gas distribution channel 46 at a different angular location about the axis of the bore 30 (as viewed in a transverse cross-section. The reactant gas supply channels 48a, 48b, 48c also connect with the bore 30 at different angular locations about the axis of the bore 30 (as viewed in a transverse cross-section), and at an angle with respect to the longitudinal axis of the bore 30 (as viewed in a longitudinal cross-section). Each of the reactant gas supply channels 48a, 48b, 48c connects with the bore 30 at a location which is angularly offset from where the reactant gas supply channels 52a, 52b, 52c connect with the bore. The reactant gas supply channels 48a, 48b, 48c also connect with the bore 30 at a greater angle than the reactant gas supply channels 52a, 52b, 52c due to the reactant gas distribution channel 46 being a greater distance from the bore 30 than the reactant gas distribution channel 50. Additionally, the bore 30 widens at the tapered portion 34 where the reactant gas supply channels 52a, 52b, 52c, 48a, 48b, 48c merge with the bore 30. This allows a smoother merger and mixing of the reactants entering at this point with flow of gas (e.g., inert gas) that enters at upstream portions of the bore 30.
Thus, in the flow pathway 1 shown in
In some embodiments, vapor deposition uniformity can be improved by providing an at least partially annular slit in an inner wall of the bore to supply gases to the bore. For example, in various embodiments, the bore can comprise a first axial portion extending along a longitudinal axis of the manifold. A supply channel can be in fluid communication between a gas source (e.g., a reactant gas source) and the bore. The supply channel can comprise a slit defining an at least partially annular gap through the inner wall of the bore to deliver a gas from the gas source to the bore. The at least partially annular gap can be revolved about the longitudinal axis of the manifold.
In addition, or alternatively, an at least partially annular flow pathway can be created in the bore to deliver gases along a longitudinal axis of the manifold. For example, a supply channel can be in fluid communication between a gas source (e.g., a reactant gas source) and the bore. The bore can comprise a channel having an annular flow portion with an at least partially annular cross-section and a non-annular flow portion with a non-annular cross-section. The non-annular cross-section can be disposed downstream of the annular flow portion.
Mounted on the body 102 are two valve blocks 112a, 112b. An inert gas valve 114a and a reactant gas valve 116a are mounted on the valve block 112a. An inert gas valve 114b and a reactant gas valve 116b are mounted on the valve block 112b. Each of the valve blocks 112a, 112b can include a reactant gas inlet 118a, 118b. At upper block 104, the manifold body 102 includes two inert gas inlets 120, 122. The reactant gas inlets 118a, 118b can be connected to different reactant sources, some of which may be naturally gaseous (i.e., gaseous at room temperature and atmospheric pressure), and some of which may be solid or liquid under standard conditions.
The body 102 can also include one or more heaters 128. Each of the valve blocks 112a, 112b can also include one or more heaters 126. The heaters 126, 128 can be disposed in such a manner as to maintain as constant a temperature as possible throughout the body 102 and/or the valve blocks. The heaters 126, 128 can be any type of heater that can operate at high temperatures suitable for ALD processes, including without limitation linear rod-style, heater jacket, heater blank, heat trace tape, or coiled resistance heaters.
A first reactant gas source 850a can connect with a distribution channel 136 in the body 102 via a passageway 137. The distribution channel 136 can be formed by lower and upper surfaces, respectively, of the upper block 104 and the intermediate block 106, and can extend in a plane that intersects with the longitudinal axis of the bore 130. For example, in some embodiments, the distribution channel 136 can be revolved at least partially (e.g., entirely) about the longitudinal axis Z of the manifold 100. The distribution channel 136 can be in fluid communication with the bore 130 via a supply channel 138 comprising a slit through an inner wall 103 defined by the bore 130.
The inert gas inlet 122 (see also
With continued reference to
As shown in
While illustrated with three reactant inlets and two inert gas inlets to the manifold body 102, the number of precursor/reactant and inert gas inlets can vary in embodiments. Also, while illustrated with two each, the number of precursor/reactant valves 116a, 116b and inert gas valves 114a, 114a feeding distribution channels can vary in embodiments, depending on the particular application and the desired processing capability of the ALD system. An ALD system may include at least two reactants and gas distribution channels therefor. The valves 114a, 114b, 116a, and 116b may be any type of valve that can withstand high temperatures within the ALD hot zone. Valves 114a, 114b, 116a, and 116b may be ball valves, butterfly valves, check valves, gate valves, globe valves or the like. Metal diaphragm valves may also be used, and may be preferred for a high temperature environment (e.g., in temperatures up to about 220° C.). In some embodiments, the valves 114a, 114b, 116a, and 116b can be, for example and without limitation, pneumatically actuated valves or piezoelectric solenoid type valves. In embodiments, the valves 114a, 114b, 116a, and 116b can be configured to operate at very high speeds, for example, with opening and closing times of less than 80 ms, with speeds of less than 10 ms in some embodiments. The valves 114a, 114b, 116a, and 116b may be formed from any material that will function at the high temperatures required for ALD processing, such as 316L stainless steel and the like. Some embodiments, such as an ALD system configured for alumina deposition, can include valves configured to operate up to 220° C. Still other embodiments can include valves configured to operate at temperatures up to 300° C., up to 400° C., or at even higher temperatures.
The manifold body 102 of
In the illustrated embodiment, three reactant sources 850a-850c are shown, although fewer or greater numbers can be provided in other arrangements. In some embodiments, one or more of the reactant sources 850a-850c can contain a naturally gaseous ALD reactant, such as H2, NH3, N2, O2, or O3. Additionally or alternatively, one or more of the reactant sources 850a-850c can include a vaporizer for vaporizing a reactant which is solid or liquid at room temperature and atmospheric pressure. The vaporizer(s) can be, e.g., liquid bubblers or solid sublimation vessels. Examples of solid or liquid reactants that can be held and vaporized in a vaporizer include, without limitation, liquid organometallic precursors such as trimethylaluminum (TMA), TEMAHf, or TEMAZr; liquid semiconductor precursors, such as dichlorosilane (DCS), trichlorosilane (TCS), trisilane, organic silanes, or TiCl4; and powdered precursors, such as ZrCl4 or HfCl4. The skilled artisan will appreciate that embodiments can include any desired combination and arrangement of naturally gaseous, solid or liquid reactant sources.
As shown in
The semiconductor processing device 10 can also include at least one controller 860, including processor(s) and memory with programming for controlling various components of the device 10. While shown schematically as connected to the reaction chamber 810, the skilled artisan will appreciate that the controller 860 communicates with various components of the reactor, such as vapor control valves, heating systems, gate valves, robot wafer carriers, etc., to carry out deposition processes. In operation, the controller 860 can arrange for a substrate 829 (such as a semiconductor wafer) to be loaded onto the substrate support 828, and for the reaction chamber 810 to be closed, purged and typically pumped down in readiness for deposition processes, particularly atomic layer deposition (ALD). A typical ALD sequence will now be described with reference to the reactor components of
In one embodiment, prior to reactant supply and during the entire ALD process, purge gas flows through the top inlet 120 into the bore 130. When the controller instructs a first ALD reactant pulse, for example from the reactant source 850b, the reactant valve 116a is open to permit flow from the reactant source 850a into the passageway 144a and around the distribution channel 146. Backpressure within the distribution channel 146 enables distribution of the gas through the supply channel 148 leading from the distribution channel 146 to the bore 130, where the first reactant merges with the inert gas flow from the inlet 120. At the same time, inert gas can flow through all other reactant channels (e.g., the reactant distribution channel 136, the supply channel 138, the reactant distribution channel 150 and supply channel 152) into the bore 130. From the bore 130, the mixture of inert gas and first reactant is fed to the showerhead plenum 824 and distributed across the showerhead plate 822 (or other dispersion mechanism) and into the reaction space 826. During this first reactant pulse, the narrower portion of the bore 130 upstream of the tapered portion 134 is filled with flowing inert gas and prevents upstream diffusion of the reactant.
After a sufficient duration to saturate the substrate 829 surface with the first reactant, the controller 860 switches off the reactant valve 116a, opens the inert gas valve 114a, and thus purges the reactant valve 116a, the passageway 144a, the reactant distribution channel 146 and the depending supply channel 148. Inert gas can continue to be supplied through the bore 130 from the top inlet 120 and the other reactant pathways for a sufficient duration to purge the manifold 100, the showerhead plenum 824, and the reaction space 826 of any remaining first reactant and/or byproduct. The skilled artisan will appreciate that other reactant removal procedures can be used in place of or in addition to purging.
After a suitably long removal period to avoid interaction of the first reactant with the subsequent reactant, the controller 860 can instruct control valves to supply a second ALD reactant from, e.g., the gaseous reactant source 850a, into the reactant passageway 137 and the upper reactant distribution channel 136. Backpressure within the distribution channel 136 enables distribution of the gas through the supply channel 138 leading from the distribution channel 136 to the bore 130, where the second reactant merges with the inert gas flow. At the same time, inert gas can flow through all other reactant channels (e.g., the reactant distribution channel 146, the supply channel 148, the reactant distribution channel 150 and supply channel 152) into the bore 130. From the bore 130, the mixture of inert gas and second reactant is fed to the showerhead plenum 824 and distributed across the showerhead plate 822 (or other dispersion mechanism) and into the reaction space 826. During this second reactant pulse, the portion of the bore 130 upstream of its merger with the supply channel 138 is filled with flowing inert gas, which prevents upstream diffusion of the second reactant. Similarly, the flow of inert gas through all other reactant flow paths prevents backwards diffusion of the second reactant.
Following saturative surface reaction on the substrate, a removal step similar to the purge step described above can be performed, including purging of the distribution channel 136 and its depending supply channel 138. The above described cycle can be repeated with the reactant distribution channel 150 and supply channel 152 to supply a third reactant gas to the substrate 829. The cycle can be further repeated until a sufficiently thick layer is formed on the substrate 829.
As shown in
The gaps 107a, 107b defined by the slits 105a, 105b can comprise a narrow opening having a thickness less than a circumferential length of the slits 105a, 105b. That is, the arc length of the slits 105a, 105b along a perimeter or circumference of the inner wall 103 (i.e., about the axis Z) can be greater than the thickness of the gaps 107a, 107b. In some embodiments, the thickness of the gaps 107a, 107b can be in a range of 0.05 mm to 1.5 mm, or more particularly, in a range of 0.1 mm to 1 mm, in a range of 0.1 mm to 0.7 mm. In some embodiments, the thickness of the gaps 107a, 107b can be in a range of 0.05 mm to 0.5 mm, e.g., in a range of 0.1 mm to 0.5 mm, in a range of 0.1 mm to 0.3 mm, or in a range of 0.2 mm to 0.3 mm, or about 0.25 mm in some embodiments. In some embodiments, the thickness of the gaps 107a, 107b can be in a range of 0.3 mm to 1.5 mm, e.g., in a range of 0.3 mm to 1 mm, in a range of 0.3 mm to 0.7 mm, or in a range of 0.4 mm to 0.6 mm, or about 0.5 mm in some embodiments.
By contrast, the thickness of the distribution channels 146, 150 along the axis Z can be significantly greater than the thickness of the gaps 107a, 107b. For example, the thickness of the distribution channels 146, 150 can be at least twice as thick as the gaps 107a, 107b, at least five times as thick as the gaps 107a, 107b, at least ten times as thick as the gaps 107a, 107b, at least twenty times as thick as the gaps 107a, 107b, or at least fifty times as thick as the gaps 107a, 107b. The gases inside the distribution channels 146, 150 can have a backpressure caused by the restriction in thickness provided by the narrow gaps 107a, 107b. The backpressure can beneficially push the gases to the bore 130 through the gaps 107a, 107b of the slits 105a, 105b.
As shown in
The resulting patterns shown in
Although the supply channels with slits described in connection with
In particular,
In
Unlike the embodiment of
In addition, as shown in
Unlike the embodiment of
As used herein, the non-annular flow pattern and the non-annular flow portions 174A, 174B can comprise any suitable non-annular cross-section of the bore 130. For example, the non-annular flow portions 174A, 174B can define a rounded (e.g., circular or elliptical) or a polygonal cross-section in which the gases fill the entire cross-section, e.g., there is no plug or obstruction in the non-annular flow portions 174A, 174B. Rather, the gases flow through the entire cross-section of the bore 130.
By contrast, the annular flow pattern and annular flow portion 173 can comprise an annular cross-section of the bore 130, in which an interior region of the bore 130 is partially occluded so as to enable the gases to flow along the longitudinal axis Z through an annular region bounded by the inner wall 103 of the manifold 130 and an obstruction within the bore 130, e.g., the plug 170. The annular flow pattern and the cross-section of the annular portion 173 can be rounded (e.g., bounded by concentric circles or ellipses), polygonal (e.g., bounded by concentric polygons), or any other suitable annular shape. The annular cross-section may be symmetric in some embodiments. In other embodiments, the annular cross-section may be asymmetric.
Moreover, as shown in
The at least partial annular portion 173 shown in
The first inert gas I1 can transition from non-annular flow to at least partially annular flow (e.g., complete annular flow) within the annular flow portion 173 when the first inert gas I1 encounters the downstream tapered portion 170A of the plug 170. The first inert gas I1 can pass through the holes 177 and can travel downstream along the annular flow portion 173 about the outer periphery of the plug 170, e.g., between the outer periphery of the plug 170 and the inner wall 103 of the manifold body 102. As shown in a first annular flow profile A1, the first inert gas I1 can uniformly fill the annular space provided between the plug 170 and the inner wall 103 of the manifold body 102.
During an example pulse of gas to the device 10, a source gas S can be supplied to the annular portion 173 of the bore 130 by way of the distribution channel 146 and the supply channel 148. For example, as explained above, the source gas S (e.g., a reactant gas) can be delivered from the wider distribution channel 146 to the narrow slit 105a by way of backpressure built up in the channel 146. As shown in a second annular flow profile A2, the source gas S can enter uniformly about the wall 103 such that source gas S can push the inert gas I1 radially inward. In the second annular flow profile A2, the source gas S can be disposed concentrically about the inert gas I1. Beneficially, the annular flow portion 173 can promote mixing between the source gas S and the first inert gas I1, at least in part because the constricted area provided by the flow portion 173 causes the source gas S and the first inert gas I1 to intermix together.
A second inert gas I2 (such as argon) can be supplied to the annular flow portion 173 of the bore 130 by way of the third distribution channel 171 and the supply channel 172, which can comprise a narrow slit 105c defining an at least partially annular gap 107c through the wall 103 of the bore 130. Advantageously, the second inert gas I2 can push the source gas S and the first inert gas I1 towards the outer periphery of the plug 170 to enhance mixing. As shown in
The mixed gases can transition from an annular flow profile A4 to a second non-annular profile N2 downstream of the plug 170. As the mixed gases emerge into the downstream non-annular portion 174B, the gases can be sufficiently mixed so as to provide a substantially uniform concentration and/or thickness on the substrate. Thus, the embodiment shown in
In a block 502, the reactant gas can be directed from the supply channel to the bore through a slit. The slit can define an at least partially annular gap along an inner wall of the bore. The at least partially annular gap can be revolved around the longitudinal axis. For example, the slit can comprise a full annulus revolved 360° about the longitudinal axis. In other embodiments, the slit can comprise a partial annulus revolved only partially about the longitudinal axis. As explained herein, the at least partially annular gap can comprise a thickness that is significantly smaller than a circumferential or peripheral length of the gap along the wall of the manifold. Beneficially, as explained herein, the slit can provide relatively uniform gas flow to the bore. In some embodiments, as explained herein, a plug can be provided to define an at least partially annular flow path. Non-annular flow paths can be provided upstream and downstream of the at least partially annular flow path.
Moving to a block 552, an at least partially annular flow pattern can be created in an annular flow portion of the bore such that the reactant gas flows along a longitudinal axis of the manifold with an at least partially annular cross-section. For example, in some embodiments, the at least partially annular flow pattern can be defined by a plug (such as the plug 170) disposed within the bore. The plug can partially obstruct the bore to divide the gas flow such that the gas flows about an outer periphery of the plug. As explained herein, upstream of the at least partially annular cross-section, the gas can flow in an upstream non-annular flow pattern. When the gas reaches the annular flow portion, the gas can flow around the outer periphery of the plug. The constricted area provided by the annular flow pathway can beneficially enhance the mixing of gases flowing through the bore.
In a block 553, downstream of the annular flow portion, a non-annular flow portion can be created in a non-annular portion of the bore such that the reactant gas flows along the longitudinal axis with a non-annular cross-section. As explained herein, the plug can comprise upstream and downstream tapered portions that can enable the transition of the gas flow from non-annular to annular, and from annular to non-annular. The convergence of the annular gas pathway into a downstream non-annular portion can further enhance mixing of supplied gases, which can advantageously improve device yield.
Various embodiments disclosed herein can enable reduce deposition non-uniformity and improve mixing by extending the mixing length along the bore 130 downstream of the location(s) at which gases are supplied to the bore 130. For example, in some embodiments, a semiconductor processing device can comprise a manifold comprising a bore therein. The bore can define a gas passageway between a first end portion of the manifold and a second end portion of the manifold. The first end portion can be disposed opposite to and spaced from the second end portion along a longitudinal axis of the manifold by a first distance. The gas passageway can extend through the manifold for a second distance larger than the first distance. For example, in some embodiments, the second distance can be at least 1.5 times the first distance, at least 2 times the first distance, at least 3 times the first distance, or at least 5 times the first distance. In some embodiments, the second distance can be in a range of 1.5 times to 10 times the first distance, e.g., in a range of 2 times to 5 times the first distance. A reaction chamber can be disposed downstream of and in fluid communication with the bore.
In some embodiments, a semiconductor processing device can include a manifold comprising a bore having an axial portion that defines a longitudinal axis of the manifold and a lateral portion extending non-parallel to the longitudinal axis. A supply channel that supplies gas to the axial portion of the bore can be disposed at a first location along the longitudinal axis. The lateral portion can be disposed at a second location downstream of the first location. The lateral portion can extend non-parallel relative to the longitudinal axis. A reaction chamber can be disposed downstream of and in fluid communication with the bore.
Beneficially, as explained herein, the sub-blocks 108a-108c can define an extending mixing length pathway 180 having a first lateral portion 180a, an offset axial portion 180b, and a second lateral portion 180b. As explained herein, the pathway 180 can provide an extended mixing length downstream of where the supply gases are introduced to the bore 130.
As explained below in connection with
The pathway 180 can extend the mixing length (and therefore mixing time) of the supplied gases as compared with a bore that extends straight through the manifold 100 along the longitudinal axis Z. As explained herein, the extended length pathway 180 can comprise the first lateral portion 180a which extends non-parallel to and away from the longitudinal axis Z, the offset axial portion 180b which extends generally parallel to, but offset from, the longitudinal axis Z, and the second lateral portion 180c which extends non-parallel to and towards the longitudinal axis Z. The second lateral portion 180c of the bore 130 can transition into a downstream axial portion 130B that extends downstream from the pathway 180 along the longitudinal axis Z to the reaction chamber 810. Although the downstream axial portion 130B is illustrated as being disposed within the manifold 100 for some length, it should be appreciated that the downstream axial portion 130B may comprise a very short length or may comprise a juncture at which the pathway 180 merges with the bore 130 at the inlet to the reaction chamber 810. That is, the second lateral portion 180c may extend laterally towards the axis Z, and an opening in the manifold may provide axial fluid communication directly between the second lateral portion 180c and the reaction chamber 810. In such an embodiment, the downstream axial portion 130B can comprise the opening or aperture which provides axial fluid communication between the pathway 180 and the reaction chamber 810.
For example,
In
In the illustrated embodiments, the extended length flow pathway 180 extends laterally away from the longitudinal axis Z, extends parallel to but offset from the axis Z, and extends laterally towards the longitudinal axis Z. In the illustrated embodiments, the first and second axial portions 130A, 130B of the bore 130 are generally aligned along the longitudinal axis Z. However, it should be appreciated that in other embodiments, the downstream axial portion 130B may be offset from the longitudinal axis Z. For example, in such embodiments, the reaction chamber 810 and the outlet 132 may be disposed offset from the inlet 120 and the axis Z. Moreover, in the illustrated embodiments, the pathway 180 includes two lateral portions 180a, 180c, and one offset axial portion 180b. In other embodiments, however, additional sub-blocks may be added to provided additional mixing length. For example, in such arrangements, the pathway 180 may comprise any suitable number of lateral portions and offset axial portions. The additional lateral and offset axial portions may further improve the mixing of the supplied gases.
The positioning of the lateral flow portions 180a, 180c, and the offset axial portion 180b can beneficially extend the mixing length of the bore 130 downstream of the location L at which the supply channels enter the bore 130. Extending the mixing length of the bore 130 can also extend the mixing time of the gases supplied to the bore 130, which can improve uniformity of deposition and improve device yield. In particular, the embodiment of
For example, as shown in
Turning to a block 702, a reactant gas can be supplied to the bore. In some embodiments, the reactant gas can be supplied to a distribution channel from a gas source. The gas can be conveyed to the bore by way of one or more supply channels extending form the distribution channel to the bore. In some embodiments, the supply channel can comprise a slit defining an at least partially annular gap through an inner wall of the bore. In other embodiments, the supply channels can comprise angled passageways that angle inwardly from the distribution channel to the bore at an acute angle.
In a block 703, the reactant gas can be directed along the gas passageway from the first end portion to the second end portion for a second distance. The second distance can be larger than the first distance. As explained herein, in some embodiments, the reactant gas can be directed along a first lateral portion extending non-parallel to and away from the longitudinal axis of the manifold. An offset axial portion of the pathway can convey the gas along the longitudinal axis. A second lateral portion can extend non-parallel to and towards the longitudinal axis of the manifold. In some arrangements, a downstream axial portion of the bore can convey the mixed gases to the reaction chamber. Advantageously, as explained herein, the extended mixing length can improve mixing and reduce non-uniformities of deposition processes.
In a block 752, the reactant gas can be directed through the axial portion of the bore parallel to the longitudinal axis. In a block 753, downstream of the axial portion, the reactant gas can be directed through the lateral portion of the bore in a direction non-parallel to the longitudinal axis. In some embodiments, the gas can pass from the lateral portion into an offset axial portion of the bore in a direction parallel to (or including a directional component parallel to) the longitudinal axis. As explained herein, a second lateral portion can extend laterally towards the longitudinal axis to convey the gas from the offset axial portion to a downstream axial portion. The gas can be conveyed along the downstream axial portion to the reaction chamber.
Various embodiments disclosed herein relate to manifolds 100 with a single reactant supply channel for each reactant gas to be supplied to the bore 100. For example, a semiconductor processing device can comprise a manifold comprising a bore defining an inner wall and a channel through the manifold. The device can include a source of a reactant gas. A supply channel can be configured to deliver the reactant gas to the bore by way of an opening on the inner wall of the bore. All the reactant gas can be delivered to the bore by the opening.
The extended mixing length provided by the pathway 180 can also advantageously enable the use of a single gas supply tier 190. Unlike the embodiments of
Although the foregoing has been described in detail by way of illustrations and examples for purposes of clarity and understanding, it is apparent to those skilled in the art that certain changes and modifications may be practiced. Therefore, the description and examples should not be construed as limiting the scope of the invention to the specific embodiments and examples described herein, but rather to also cover all modification and alternatives coming with the true scope and spirit of the invention. Moreover, not all of the features, aspects and advantages described herein above are necessarily required to practice the present invention.
Number | Name | Date | Kind |
---|---|---|---|
1523156 | Adams | Jan 1925 | A |
1853045 | Gnau | Apr 1932 | A |
3882934 | Knoos | May 1975 | A |
3913617 | van Laar | Oct 1975 | A |
4222671 | Gilmore | Sep 1980 | A |
4401052 | Baron et al. | Aug 1983 | A |
4410281 | Crookes | Oct 1983 | A |
4422773 | Cassaday | Dec 1983 | A |
4649859 | Wanlass | Mar 1987 | A |
4747367 | Posa | May 1988 | A |
4828224 | Crabb et al. | May 1989 | A |
4869284 | Scott | Sep 1989 | A |
4889609 | Cannella | Dec 1989 | A |
4895107 | Yano et al. | Jan 1990 | A |
4907534 | Huang et al. | Mar 1990 | A |
4949783 | Lakios et al. | Aug 1990 | A |
4951601 | Maydan et al. | Aug 1990 | A |
4990047 | Wagner et al. | Feb 1991 | A |
5004374 | Grey | Apr 1991 | A |
5071460 | Fujiura et al. | Dec 1991 | A |
5080549 | Goodwin et al. | Jan 1992 | A |
5106453 | Benko | Apr 1992 | A |
5121705 | Sugino | Jun 1992 | A |
5131627 | Kolenc | Jul 1992 | A |
5166092 | Mochizuki et al. | Nov 1992 | A |
5186718 | Tepman et al. | Feb 1993 | A |
5192371 | Shuto et al. | Mar 1993 | A |
5199483 | Bahng | Apr 1993 | A |
5217501 | Fuse et al. | Jun 1993 | A |
5223001 | Saeki | Jun 1993 | A |
5229615 | Brune et al. | Jul 1993 | A |
5248253 | Philipossian et al. | Sep 1993 | A |
5252131 | Kiyama | Oct 1993 | A |
5284519 | Gadgil | Feb 1994 | A |
5286296 | Sato et al. | Feb 1994 | A |
5288327 | Bhat | Feb 1994 | A |
5350453 | Scholosser | Sep 1994 | A |
5388944 | Takanabe et al. | Feb 1995 | A |
5391035 | Krueger | Feb 1995 | A |
5405446 | Nakajima | Apr 1995 | A |
5433785 | Saito | Jul 1995 | A |
5462397 | Iwabuchi | Oct 1995 | A |
5488925 | Kumada | Feb 1996 | A |
5516732 | Flegal | May 1996 | A |
5520742 | Ohkase | May 1996 | A |
5520743 | Takahashi | May 1996 | A |
5538390 | Salzman | Jul 1996 | A |
5571330 | Kyogoku | Nov 1996 | A |
5586585 | Bonora et al. | Dec 1996 | A |
5601651 | Watabe | Feb 1997 | A |
5609459 | Muka | Mar 1997 | A |
5728223 | Murakami et al. | Mar 1998 | A |
5755878 | Habuka et al. | May 1998 | A |
5789027 | Watkins et al. | Aug 1998 | A |
5846330 | Quirk | Dec 1998 | A |
5851294 | Young | Dec 1998 | A |
5885358 | Maydan | Mar 1999 | A |
5893641 | Garcia | Apr 1999 | A |
5938840 | Habuka et al. | Aug 1999 | A |
5951771 | Raney | Sep 1999 | A |
6036783 | Fukunaga et al. | Mar 2000 | A |
6070550 | Ravi et al. | Jun 2000 | A |
6079353 | Leksell et al. | Jun 2000 | A |
6114227 | Leksell et al. | Sep 2000 | A |
6217658 | Orczyk | Apr 2001 | B1 |
6224676 | Nakajima et al. | May 2001 | B1 |
6299692 | Ku et al. | Oct 2001 | B1 |
6302965 | Umotoy et al. | Oct 2001 | B1 |
6303501 | Chen et al. | Oct 2001 | B1 |
6331072 | Schierholz | Dec 2001 | B1 |
6375750 | van Os | Apr 2002 | B1 |
6416213 | Fukunaga | Jul 2002 | B1 |
6534133 | Kaloyeros et al. | Mar 2003 | B1 |
6660177 | Carr | Dec 2003 | B2 |
6783590 | Lindfors et al. | Aug 2004 | B2 |
6846516 | Yang et al. | Jan 2005 | B2 |
6881263 | Lindfors et al. | Apr 2005 | B2 |
6884296 | Basceri et al. | Apr 2005 | B2 |
6899507 | Yamagishi et al. | May 2005 | B2 |
6905547 | Londergan et al. | Jun 2005 | B1 |
6916398 | Chen et al. | Jul 2005 | B2 |
7018478 | Lindfors et al. | Mar 2006 | B2 |
7021881 | Yamagishi et al. | Apr 2006 | B2 |
7045060 | Liles | May 2006 | B1 |
7163587 | Kinnard et al. | Jan 2007 | B2 |
7175713 | Thakur et al. | Feb 2007 | B2 |
7195037 | Eidsmore | Mar 2007 | B2 |
7204886 | Chen et al. | Apr 2007 | B2 |
7297892 | Kelley et al. | Nov 2007 | B2 |
7304263 | Chang et al. | Dec 2007 | B2 |
7311851 | Carr | Dec 2007 | B2 |
7402210 | Chen et al. | Jul 2008 | B2 |
7408225 | Shinriki et al. | Aug 2008 | B2 |
7591907 | Chen et al. | Sep 2009 | B2 |
7591957 | Carr | Sep 2009 | B2 |
7670399 | Park | Mar 2010 | B2 |
7780785 | Chen et al. | Aug 2010 | B2 |
7780789 | Wu et al. | Aug 2010 | B2 |
7846499 | Blomberg | Dec 2010 | B2 |
7918938 | Provencher et al. | Apr 2011 | B2 |
8070879 | Chen et al. | Dec 2011 | B2 |
8137463 | Liu et al. | Mar 2012 | B2 |
8152922 | Schmidt et al. | Apr 2012 | B2 |
8211230 | Verghese et al. | Jul 2012 | B2 |
8298336 | Wang et al. | Oct 2012 | B2 |
8372201 | Provencher et al. | Feb 2013 | B2 |
8425682 | Wang et al. | Apr 2013 | B2 |
8465801 | Schmidt et al. | Jun 2013 | B2 |
8668776 | Chen et al. | Mar 2014 | B2 |
8784563 | Schmidt et al. | Jul 2014 | B2 |
9388492 | White et al. | Jul 2016 | B2 |
9574268 | Dunn | Feb 2017 | B1 |
10147597 | Lee | Dec 2018 | B1 |
20010003015 | Chang et al. | Jun 2001 | A1 |
20010006093 | Tabuchi et al. | Jul 2001 | A1 |
20020007790 | Park | Jan 2002 | A1 |
20020072164 | Umotoy et al. | Jun 2002 | A1 |
20020081381 | DelaRosa et al. | Jun 2002 | A1 |
20020113327 | Hara | Aug 2002 | A1 |
20020170674 | Shapiro | Nov 2002 | A1 |
20020195055 | Grant et al. | Dec 2002 | A1 |
20030010451 | Tzu et al. | Jan 2003 | A1 |
20030019428 | Ku et al. | Jan 2003 | A1 |
20030056720 | Dauelsberg et al. | Mar 2003 | A1 |
20030070620 | Cooperberg et al. | Apr 2003 | A1 |
20030079686 | Chen et al. | May 2003 | A1 |
20030101938 | Ronsse et al. | Jun 2003 | A1 |
20030106643 | Tabuchi et al. | Jun 2003 | A1 |
20030172872 | Thakur et al. | Sep 2003 | A1 |
20030180460 | Strauch et al. | Sep 2003 | A1 |
20030194360 | Huziwara | Oct 2003 | A1 |
20030205096 | Gehner | Nov 2003 | A1 |
20040028810 | Grant et al. | Feb 2004 | A1 |
20040035358 | Basceri et al. | Feb 2004 | A1 |
20040113289 | Toda | Jun 2004 | A1 |
20040118342 | Cheng et al. | Jun 2004 | A1 |
20040144311 | Chen | Jul 2004 | A1 |
20040197090 | Kudo | Oct 2004 | A1 |
20040217217 | Han | Nov 2004 | A1 |
20050000428 | Shero et al. | Jan 2005 | A1 |
20050000656 | Carr | Jan 2005 | A1 |
20050009325 | Chung et al. | Jan 2005 | A1 |
20050092247 | Schmidt et al. | May 2005 | A1 |
20050173068 | Chen et al. | Aug 2005 | A1 |
20050208217 | Shinriki et al. | Sep 2005 | A1 |
20050252449 | Nguyen et al. | Nov 2005 | A1 |
20050263197 | Eidsmore | Dec 2005 | A1 |
20050271812 | Myo et al. | Dec 2005 | A1 |
20060053833 | Martins | Mar 2006 | A1 |
20060096540 | Choi | May 2006 | A1 |
20060266289 | Verghese et al. | Nov 2006 | A1 |
20070001326 | Toda | Jan 2007 | A1 |
20070026147 | Chen et al. | Feb 2007 | A1 |
20070095285 | Thakur et al. | May 2007 | A1 |
20070128864 | Ma et al. | Jun 2007 | A1 |
20070187634 | Sneh | Aug 2007 | A1 |
20070194470 | Dedontney | Aug 2007 | A1 |
20080037968 | Kaastra | Feb 2008 | A1 |
20080085226 | Fondurulia et al. | Apr 2008 | A1 |
20080102203 | Wu et al. | May 2008 | A1 |
20080102208 | Wu et al. | May 2008 | A1 |
20080115740 | You | May 2008 | A1 |
20080162580 | Ben Harush | Jul 2008 | A1 |
20080202416 | Provencher et al. | Aug 2008 | A1 |
20080271610 | Vedsted | Nov 2008 | A1 |
20090095222 | Tam | Apr 2009 | A1 |
20090196992 | Schmidt et al. | Aug 2009 | A1 |
20090215912 | Goto | Aug 2009 | A1 |
20090320754 | Oya | Dec 2009 | A1 |
20100003406 | Lam et al. | Jan 2010 | A1 |
20100024727 | Kim et al. | Feb 2010 | A1 |
20100048032 | Sangam et al. | Feb 2010 | A1 |
20100092163 | Yeung | Apr 2010 | A1 |
20100150756 | Chow | Jun 2010 | A1 |
20100266765 | White et al. | Oct 2010 | A1 |
20100296800 | Min | Nov 2010 | A1 |
20100310772 | Tsuda | Dec 2010 | A1 |
20110098841 | Tsuda | Apr 2011 | A1 |
20110111136 | Slevin | May 2011 | A1 |
20110116776 | Wheeler | May 2011 | A1 |
20110128814 | Hanada | Jun 2011 | A1 |
20110199855 | Hanada | Aug 2011 | A1 |
20110223334 | Yudovsky | Sep 2011 | A1 |
20120079984 | Schmidt et al. | Apr 2012 | A1 |
20120289057 | DeDontney | Nov 2012 | A1 |
20130058835 | Salazar-Guillen | Mar 2013 | A1 |
20130061759 | Laor | Mar 2013 | A1 |
20130160709 | White et al. | Jun 2013 | A1 |
20130206338 | Tanaka | Aug 2013 | A1 |
20130333620 | Li | Dec 2013 | A1 |
20140261178 | Du Bois et al. | Sep 2014 | A1 |
20140284404 | Kuah | Sep 2014 | A1 |
20150104161 | De Mango | Apr 2015 | A1 |
20150176126 | Ge | Jun 2015 | A1 |
20150232355 | Ghaffour | Aug 2015 | A1 |
20150240359 | Jdira | Aug 2015 | A1 |
20150371831 | Rozenzon | Dec 2015 | A1 |
20150377481 | Smith | Dec 2015 | A1 |
20160222508 | Schoepp | Aug 2016 | A1 |
20160281232 | White et al. | Sep 2016 | A1 |
20170121818 | Dunn | May 2017 | A1 |
20170350011 | Marquardt | Dec 2017 | A1 |
Number | Date | Country |
---|---|---|
3715644 | Dec 1988 | DE |
H09-186111 | Jul 1997 | JP |
4667541 | Apr 2011 | JP |
WO 9010092 | Sep 1990 | WO |
WO 0129282 | Apr 2001 | WO |
WO-2010047168 | Apr 2010 | WO |
WO-2014163742 | Oct 2014 | WO |
Entry |
---|
Office Action for Chinese Patent Application No. 200780002793.9, dated Mar. 15, 2010. |
Office Action for Chinese Patent Application No. 200780002793.9, dated Apr. 19, 2011. |
Notice for Reasons for Rejection dated Feb. 28, 2012 for Japanese Patent Application No. 2008551324, filed Jul. 16, 2008, 5 pages. |
Number | Date | Country | |
---|---|---|---|
20170350011 A1 | Dec 2017 | US |