Method and system for integrated synthesis, delivery and processing of chemical sources for thin film manufacturing - Patents.com

Abstract

To provide an integrated system for synthesis of a film-forming precursor, consumption of the precursor and formation of a thin film on a substrate.SOLUTION: The integrated system includes a raw material source, a precursor synthesis chamber in communication with the raw material source, a thin film processing chamber in communication with the precursor synthesis chamber for supplying the precursor from the precursor synthesis chamber to the thin film processing chamber in a controlled manner for consumption of the precursor to form the thin film on the substrate, a monitoring system for monitoring of the thin film formation in the thin film processing chamber and / or the precursor synthesis in the precursor synthesis chamber, and a controller for controlling a rate of the precursor synthesis, precursor consumption and / or thin film formation. The rate of precursor synthesis is synchronized with the rate of precursor consumption for formation of the thin film.SELECTED DRAWING: Figure 1

Description

Detailed Description of the Invention

[0001] [CROSS-REFERENCE TO RELATED APPLICATIONS]

[0002] This application claims priority to U.S. Provisional Patent Application No. 62 / 571,439, filed October 12, 2017, the disclosure of which is incorporated herein by reference.

[0002] [Background of the invention]

[0003] The present invention includes methods and integrated systems for the synthesis, transport and delivery of chemical sources, and processing for thin film manufacturing, including, for example, deposition, etching, and patterning.

[0003]

[0004] Across multiple industries, including integrated circuit (IC) devices and microelectromechanical systems (MEMS), conventional thin film manufacturing methods, including but not limited to chemical vapor deposition (CVD), atomic layer deposition (ALD), liquid plating, etching (including atomic layer etching, partial and full material removal processes), implantation (e.g., ion implantation), and patterning (i.e., forming a predetermined structure in a previously deposited layer, e.g., a transistor pattern in a silicon substrate), primarily involve the following five-step approach: (1) producing or synthesizing a precursor at a first location, e.g., a chemical manufacturing plant; (2) then transporting the precursor to a customer until the precursor is ready to be shipped to the customer. (3) the precursor is then transported by land, air or sea transportation from the leak- and spill-proof custom container or custom storage facility to a second location, typically a customer's industrial plant, where the precursor will be used in the manufacture of a device or system; (4) the precursor remains stored in the leak- and spill-proof custom container or custom storage facility at the second location until the precursor is ready to be used; (5) finally, the precursor is introduced into a manufacturing process being carried out at the second location such that the precursor may be applied or consumed in the growth, construction or formation of a thin film as part of a device or system fabrication technique.

[0004]

[0005] However, the conventional manufacturing methods discussed above have various technical, safety, environmental and economic inefficiencies and drawbacks. Conventional manufacturing methods are limited by the risk of bulk storage or the need for extensive cooling to preserve their integrity before use, for example by the inability to transport chemicals that have harmful inhalation toxicity and / or are unstable due to impact sensitivity. Another major drawback is the unnecessarily long time window and long duration that elapses between the synthesis of the precursor and the actual use of the precursor. This drawback results in a large economic burden due to the capital expenditure associated with the need to store and preserve expensive precursors at the chemical synthesis facility before the precursor is sold and shipped to the customer facility for use. The present protocol also requires the use of specialized containers to preserve the integrity of the precursor until it is used, which is another added cost. Redundancies are associated with storage and transportation at both the precursor synthesis and consumption facilities. Huge additional costs are incurred due to the double handling, storage, treatment and disposal of by-products from the precursor synthesis at the precursor synthesis facility and the precursor consumption at the customer facility. Additionally, concerns about changes in product quality over time can result in additional costs to ensure that products do not deviate from intended technical specifications from the point of manufacture to the point of consumption.

[0005]

[0006] Equally important are the environmental, safety and health threats associated with the transport of chemicals by air, sea or land, and the resulting devastating human and environmental impacts that could result from the release of chemicals due to, for example, human error, failure of quality controls and / or other unforeseen events that may occur during the transportation and handling phase.

[0006]

[0007] These disadvantages and shortcomings are exemplified in the semiconductor (i.e., computer chip) and heterogeneous integrated circuit (IC) industries, where many of these conventional manufacturing methods are used in what are commonly referred to as batch, stand-alone, and cluster tool manufacturing or processing equipment. Batch tool processing involves the simultaneous application of a manufacturing technique to multiple wafers in a single manufacturing equipment. In contrast, stand-alone tool processing involves the application of a manufacturing technique to a single wafer in an individual piece of equipment before transporting the wafer to a different batch, stand-alone, or cluster tool manufacturing equipment. Cluster tool processing, on the other hand, involves several single wafer processing chambers and wafer handling robots.

[0007]

[0008] Cluster tool processing has been increasingly used in various wafer fabrication processes in recent years, as described in a paper by A. Bowling entitled "Single-Wafer Processing And Real-Time Process Control For Semiconductor Integrated Circuit Manufacturing" published at the International Symposium on Semiconductor Manufacturing (A. Bowling, Int'l. Symposium on Semiconductor Mfg., (June 21-22, 1994, IEEE)). The last successful introduction of a large-scale new manufacturing equipment methodology in the IC industry was the introduction of single-wafer cluster tools by Applied Materials in the mid-1980s. Cluster tool-based manufacturing replaced most of the batch processing protocols that were prevalent at that time, allowing the IC industry to reduce total manufacturing costs, incorporate computer-controlled sensors into the manufacturing equipment to provide real-time diagnostics, achieve multiplicity in the simultaneous execution of different manufacturing recipes, ensure fast manufacturing cycle times, implement short-loop manufacturing cycles to test material and process innovations, and achieve flexibility in the simultaneous fabrication of various IC products. These achievements are described, for example, on the Applied Materials website and in articles by MM Moslehi et al. and SMGeorge et al. (MM Moslehi et al., "Single-Wafer Integrated Semiconductor Device Processing", IEEE Transactions on Electron Devices, V. 39, pp. 4-31 (1992); SMGeorge, "Atomic Layer Deposition: An Overview", Chem. Rev., V. 110, pp. 111-131 (2010)).

[0008]

[0009] The acceptance of cluster tool fabrication methods is based on the need for sequential processes such as CVD and ALD processes that require strict control of processing parameters including exposure time, pressure, temperature and other parameters. For example, cluster tools are typically formed with multiple wafer processing stations arranged around a central automated handling unit with fixed inlets for precursors that are delivered to each processing station, such as the deposition chamber. The inlets are typically stable reservoirs of gas or volatile materials. The wafers processed in the first deposition chamber then leave the first deposition chamber within a specified time limit and are typically transferred, in-situ, under high vacuum conditions and without vacuum break, to another deposition chamber in the cluster tool.

[0009]

[0010] Without in-situ, high vacuum conditions, the device structures being built on the wafer would be subject to quality issues due to residual precursor gases and by-products, heat in the initial deposition chamber, cross-contamination issues with other deposition precursors or precursor by-products, oxidation and inclusion of external contaminants if the wafer is exposed to air while being transported from one chamber to the next, etc. In-situ transfer between processing stations under vacuum allows for tight control of the atmosphere or environment to ensure control, virtually eliminating contamination between process steps.

[0010]

[0011] However, the generation and delivery of the precursors is independent of the cluster tool. Thus, the high level of automation and control utilized in cluster tools does not extend to the generation of the precursors themselves, but rather only to the controlled delivery or delivery of the precursors to the deposition chamber. Furthermore, this modality is inherently dependent on maintaining the thermal stability and chemical integrity of the precursors under storage conditions until the point of use.

[0011]

[0012] In addition, the well-established movement towards more complex and smaller semiconductor and heterodevice structures is causing increasing limitations in established thin film deposition methods. In particular, low temperature exposure during the fabrication of device structures is becoming essential due to their complexity and thermal fragility, where temperature changes can induce undesired reactions within the substructures. This threat is described, for example, in papers by M. Badaroglu (M. Badaroglu, ITRS Summer Conference, Roadmap Meeting, Stanford University, July 11-12, 2015; and International Technology Roadmap for Semiconductors 2.0, 2015 Edition, Interconnect). Furthermore, as film thickness approaches atomic dimensions, thermally induced migration in addition to electrical migration can alter film properties and performance.

[0012]

[0013] Another consideration is the desire to move to more flexible substrates, e.g., plastic or polymer substrates, which typically cannot withstand the same process temperatures as traditional substrates such as silicon nitride or gallium nitride. See, e.g., S. Majee et al., "Permeation barrier performance of Hot Wire-CVD grown silicon-nitride films treated by argon plasma," Thin Solid Films, V. 575, pp. 72-75 (2015).

[0013]

[0014] Yet another consequence of the push towards more complex and smaller fabricated structures is the move to incorporate new materials and process technologies. Whereas semiconductors in the 1990s utilized a maximum of approximately 12 atomic elements, the International Technology Roadmap for Semiconductors predicts that in 2015 semiconductor manufacturing will use nearly 50 atomic elements. See, for example, B. Bottoms et al., ITRS Summer Conference, Roadmap Meeting, Stanford University, July 11-12, 2015; R. Allen et al., ITRS Summer Conference, Roadmap Meeting, Stanford University, July 11-12, 2015; S. Das, ITRS Architecture Workshop, February 26-27, 2015. Considering the compounds that result from the possible combinations of these various atomic elements, the diversity and complexity of materials (e.g., metals, semiconductors, insulators, dielectrics, etc.) is growing at a nearly exponential rate. However, this growth is severely limited by the inability to develop storage-stable, transportable sources of volatile precursors that can be controllably and reliably reacted to form high quality films within the processing stations of manufacturing equipment.

[0014]

[0015] A further consequence of the move towards more complex and smaller fabricated structures is the increasing costs associated with the manufacture of such structures due to their complexity, the introduction of new materials and process technologies, and the need for extreme precision and tight control in the formation of ultra-thin films (e.g., atomic layer thin).

[0015]

[0016] Therefore, methods and systems for synthesis, delivery and processing of precursors for thin film production that eliminate or reduce the number of extra steps in the manufacturing process, thus lowering the manufacturing costs of both conventional and new materials and processes, would be desirable. Furthermore, a method that eliminates the thermal and chemical stability issues of precursors would expand the ability to deposit new and desirable thin film compositions that are not currently available with conventional methods and systems. Furthermore, such methods and systems would be highly desirable in multiple industry sectors, including the semiconductor (e.g., computer chips), aircraft, energy, sensors, medical, biological, chemical and defense industry sectors.

[0016] [Brief Summary of the Invention]

[0017] In one embodiment, the present invention relates to an integrated system for synthesis of film-forming precursors, consumption of the precursors and formation of thin films on a substrate, wherein the precursor synthesis rate is synchronized with the precursor consumption rate for formation of the thin film.

[0017]

[0018] In another embodiment, the present invention relates to an integrated system for the synthesis of film-forming precursors, the consumption of the precursors, and the formation of thin films on substrates, comprising: a raw material source containing at least one raw material; a precursor synthesis chamber having an inlet and an outlet, the inlet of the precursor synthesis chamber being in communication with the raw material source for supplying the raw material to the precursor synthesis chamber where the raw material reacts to synthesize a precursor; a thin film processing chamber coupled to the precursor synthesis chamber, the thin film processing chamber having an inlet in direct communication with and coupled to the outlet of the precursor synthesis chamber for supplying the precursor from the precursor synthesis chamber to the thin film processing chamber in a controlled manner to consume the precursor in the thin film processing chamber to form a thin film on a substrate; a monitoring system for real-time monitoring and detection of the endpoint of precursor synthesis in the thin film formation and / or precursor synthesis chamber; and (i) a controller for receiving data on precursor consumption and thin film formation from the monitoring system and sending the data to the precursor synthesis chamber to control the rate of precursor synthesis to ensure that the precursor synthesis rate matches the demands of precursor consumption and thin film formation, and / or (ii) a controller for receiving data on precursor synthesis from the monitoring system and sending the data to the thin film processing chamber to control the rate of precursor consumption and thin film formation to ensure that the rate of precursor consumption and thin film formation matches the precursor synthesis rate, the precursor synthesis rate being synchronized with the precursor consumption rate for the formation of the thin film.

[0018]

[0019] In another embodiment, the present invention relates to an integrated method for the synthesis of film-forming precursors, consumption of the precursors, and formation of thin films on a substrate. The integrated method includes the steps of: providing, at a first location, a raw material source containing at least one raw material; delivering, at the first location, the at least one raw material from the raw material source to a precursor synthesis chamber; reacting, at the first location, the at least one raw material in the precursor synthesis chamber to form a precursor; delivering, at the first location, the precursor from the precursor synthesis chamber in a controlled manner to a thin film processing chamber operating in tandem with and coupled to the precursor synthesis chamber; applying, at the first location, a manufacturing technique for the consumption of the precursor to form a thin film on a substrate disposed in the thin film processing chamber; performing endpoint real-time monitoring and detection of precursor consumption and thin film formation in the thin film processing chamber; and providing feedback regarding precursor consumption and thin film formation to the precursor synthesis chamber to control the synthesis of the precursor such that (i) the synthesis of the precursor occurs simultaneously or in tandem with thin film formation, (ii) the precursor synthesis rate matches the demand for precursor consumption and thin film formation, and (iii) the precursor synthesis rate is synchronized with the precursor consumption rate for the formation of the thin film.

[0019]

[0020] In another embodiment, the present invention relates to an integrated method for the generation of nickel carbonyl precursors and the formation of nickel thin films on substrates. The method includes the steps of: at a first location, providing bulk metallic nickel to a precursor generation chamber; sealing the precursor generation chamber; purging the precursor generation chamber to evacuate absorbed and residual gases; heating the bulk metallic nickel to a temperature between 80° C. and 120° C.; providing carbon monoxide to the precursor generation chamber while enabling flow communication between the precursor generation system and a downstream interconnected thin film processing chamber to generate a nickel carbonyl precursor and providing the nickel carbonyl precursor directly from the precursor generation chamber to the thin film processing chamber; heating a substrate in the thin film processing chamber to a temperature between 180° C. and 250° C. such that the nickel carbonyl precursor decomposes at the substrate to form a nickel thin film; performing real-time in-situ monitoring and detection of the end point of nickel thin film formation in the thin film processing chamber; and providing feedback regarding nickel thin film formation to the precursor generation chamber to control the rate of generation of the nickel carbonyl precursor such that the generation of the nickel carbonyl precursor occurs simultaneously or in tandem with nickel thin film formation.

[0020]

[0021] In another embodiment, the invention relates to an integrated method for the production of hydrazoic acid precursors and the formation of silicon nitride thin films on silicon substrates. The method includes providing a high boiling point hydroxylic liquid to a precursor production chamber having a gas inlet adjacent a lower end of the chamber below the liquid level and a gas outlet above the liquid level. The method further includes the steps of heating the hydroxyl liquid to a temperature between 40°C and 65°C to form a hydroxylated liquid; introducing a first flow of trimethylsilyl azide in a carrier gas into a precursor production chamber through a gas inlet, where the trimethylsilyl azide reacts with the hydroxylated liquid to produce a hydroazoic acid precursor; delivering a second flow of hydroazoic acid in a carrier gas directly from the precursor production chamber to a thin film processing chamber operating in tandem with and connected to the precursor production chamber; heating a silicon substrate in the thin film processing chamber to a temperature between 325°C and 500°C such that the hydroazoic acid reacts with the silicon substrate to form a silicon nitride thin film; performing real-time in-situ monitoring and detection of endpoint silicon nitride thin film formation in the thin film processing chamber; and providing feedback regarding silicon nitride thin film formation to the precursor production chamber to control the generation of hydroazoic acid precursor such that the generation of hydroazoic acid precursor occurs simultaneously or in tandem with silicon nitride thin film formation.

[0021]

[0022] In another embodiment, the present invention relates to an integrated method for the production of monosilylamine precursor and the formation of silicon nitride thin film on silicon substrate, the method includes the steps of: supplying a first flow of ammonia in a first carrier gas to a precursor production chamber; supplying a second flow of monochlorosilane in a second carrier gas to the precursor production chamber to react with the first flow and produce monosilylamine precursor; supplying the monosilylamine precursor in the first and second carrier gases from the precursor production chamber to a thin film processing chamber operating in tandem with and connected to the precursor production chamber; applying a manufacturing technique for consumption of the monosilylamine precursor to form a silicon nitride thin film on a silicon substrate disposed in the thin film processing chamber; performing endpoint real-time in-situ monitoring and detection of silicon nitride thin film formation in the thin film processing chamber; and providing feedback regarding silicon nitride thin film formation to the precursor production chamber to control the production of the monosilylamine precursor such that the production of the monosilylamine precursor occurs simultaneously or in tandem with silicon nitride thin film formation.

[0022]

[0023] Yet another embodiment of the present invention relates to an integrated method of forming metal halide precursors in pulses timed to match atomic layer deposition (ALD) pulse requirements.

[0023]

[0024] The novel integration of thin film formation demands with precursor production and consumption according to the present invention allows for practical deposition of thin compositions under conditions previously thought to be impractical for integrated manufacturing. For example, for highly toxic or potentially explosive precursors, it is possible to control the physical presence of the precursors below toxicity or self-accelerating decomposition hazard limits so that they are immediately consumed in the manufacturing process. Also, because the first and second chambers are linked together and communicate with each other using a tightly controlled valve and pump system, the integrity of the internal atmosphere of each chamber is maintained and isolated, while still allowing precise flow of gases, chemicals and precursors between the chambers.

[0024]

[0025] The novel integration of thin film formation demand requirements with precursor production and consumption according to the present invention also enables the use of chemicals and precursors that are too unstable at room temperature or that require extensive cooling to preserve their integrity before use. The present invention also enables the formation or volatilization of new, unconventional precursors and chemicals that are not yet commercially available and are not currently used in manufacturing. The present invention also enables the formation or volatilization of known and desirable precursors and chemicals that were previously considered too toxic, too unstable, or otherwise dangerous to utilize in commercial thin film fabrication and modification processes.

[0025]

[0026] The present invention also eliminates the unnecessary steps in conventional manufacturing methods that require the synthesis of precursors or chemicals at a first location, most commonly a chemical manufacturing plant, and then transporting the precursors to a second location, a device or system manufacturing plant, where they are consumed in the manufacturing process. More specifically, the present invention eliminates the step of transporting the synthesized precursors to the device or system manufacturing plant. In turn, the present invention also eliminates the need for costly specialized containers to preserve the integrity of the chemicals until they are used; eliminates the redundancy associated with storage and transportation at both chemical synthesis and customer facilities; and consolidates the dual handling, storage, processing and disposal of by-products from precursor synthesis at the chemical plant and precursor chemical consumption at the manufacturing plant into a single by-product disposal step at the manufacturing plant.

[0026]

[0027] The present invention is also distinct from the concept of point-of-use generation of precursors. Generally speaking, there are two classes of point-of-use precursor generation. One class involves the formation of precursors in-situ in the same chamber where thin film fabrication takes place, usually in the vapor space above the substrate. This class is sometimes referred to as "in-situ point-of-use precursor generation." The second class involves the generation of precursors in a container in close proximity to the thin film processing or fabrication chamber, where the precursors are either immediately delivered to the fabrication chamber or are stored / stored until use at a later time. This class is sometimes referred to as "ex-situ" or "proximal" point-of-use precursor generation.

[0027]

[0028] Both in-situ and ex-situ point-of-use precursor generation have some inherent limitations and disadvantages. Examples of in-situ precursor generation are disclosed in U.S. Pat. No. 6,730,367 and U.S. Pat. No. 5,478,435. One inherent limitation of in-situ precursor generation is that the chemical reactions associated with precursor synthesis often interfere with the chemical reactions associated with thin film fabrication. Also, precise control of processing conditions is difficult to achieve in in-situ point-of-use precursor generation due to the inherent characteristics of the precursor synthesis chemical reactions, which may include the presence of starting materials, the generation of by-products, and heat or light from the reaction of multiple basic chemical components required to synthesize the precursor. Such side effects of the precursor synthesis reactions can directly affect film formation and negatively impact the processing chamber, including adverse effects on chamber walls and substrate operating parameters, such as undesirable and uncontrollable increases in the temperature of the reaction walls and / or substrate, and heat- or light-induced damage to fragile substrates such as plastics and polymers. The present invention provides a much more reliable and highly reproducible approach since the basic chemical components are injected into separate synthesis chambers, where the actual chemical reactions take place, and only the resulting precursors are introduced into the processing reactor.

[0028]

[0029] Another limitation of in-situ point-of-use generation of precursors is the sequential nature of the synthesis and processing steps involved. In a first step, the processing chamber needs to be set to specific precursor synthesis parameters to allow multiple basic components to react near or within the chamber to form the precursor source. Then, the processing chamber is purged to remove all synthesis by-products, and finally, the processing chamber is set to the actual substrate processing parameters (including substrate introduction) to allow precursor decomposition and film formation. However, this approach causes undesirable delays in wafer throughput (and therefore higher manufacturing costs) due to the successive steps of precursor formation in the processing chamber at a first set of parameters, then waiting for these parameters to change to allow decomposition and film formation.

[0029]

[0030] The present invention solves these problems by sequentially synthesizing the precursor sources in separate synthesis chambers and controllably and reliably feeding the precursor sources continuously into a process chamber preset to the desired process parameters, where the precursor sources are simultaneously consumed in the creation or deposition process.

[0030]

[0031] A further limitation of in situ point-of-use generation of precursors are issues associated with precursor synthesis by-products, rather than contamination of the process chamber and substrate. The present invention solves these problems by removing precursor synthesis by-products, if necessary, from the precursor synthesis chamber prior to introduction of the precursor into the process chamber.

[0031]

[0032] Yet another limitation of in situ point-of-use generation of precursors is the concern that the base chemical components for the synthesis of the precursors and the by-products of such synthesis may be harmful or damaging to the processing chamber, as they may cause undesirable etching, corrosion or oxidation of the fabrication chamber. The present invention solves these problems by synthesizing the precursor sources in separate synthesis chambers specially designed and constructed to handle corrosive, oxidizing or otherwise interfering base chemicals and reaction by-products, and by removing the precursor synthesis by-products prior to introduction of the precursors into the processing chamber.

[0032]

[0033] A further limitation of in situ point-of-use generation of precursors is that precursor synthesis is not coupled with precursor consumption in the manufacturing process, which limits the ability to precisely control the manufacturing process to obtain precise deposition results, such as thin films of precise thickness and composition. Precise coupling of precursor generation and deposition process with a mechanical feedback loop is a key aspect of the present invention, as described in detail herein.

[0033]

[0034] Examples of ex-situ or near-point-of-use precursor generation are disclosed in JP ven der Ziel, Applied Physics Letters, Vol. 71:6, pp. 791-793 (1997); DN Buckley et al., Applied Physics Letters, Vol. 57:16, pp. 1684-1686 (1990); U.S. Patent No. 5,158,656; and U.S. Patent Application Publication No. 2011 / 0136347. The main limitation of ex-situ point-of-use generation of precursors is that precursor synthesis is not tightly coupled or synchronized with precursor consumption in the manufacturing process, which severely limits the ability to precisely control the manufacturing process to obtain precise deposition results, such as thin films of precise thickness, desired morphology, physical and chemical properties, and composition. For the ever-increasing importance of control in new manufacturing processes, see, for example, A. Emami-Naeini et al., Proceedings of the Symposium to honor W. Wolovich, 47th IEEE Conference on Decision and Control, Cancun, Mexico, December 9-11, 2008. Precise linking of precursor generation and deposition processes with a machine-based feedback loop is a key aspect of the present invention, as described in detail herein.

[0034]

[0035] The machine-based feedback loops may include in-situ and ex-situ monitoring and detection techniques, spectroscopy, and spectrometry for the simultaneous monitoring, control, and management and pairing of various parameters of the precursor synthesis process and the film manufacturing process. Such parameters may include, but are not limited to, temperature, pressure, flow rates of raw materials and precursors, and all operating conditions of the chemical synthesis production itself and the thin film manufacturing process. In-situ and ex-situ detection techniques, spectroscopy and spectrometry also allow for endpoint real-time in-situ monitoring and detection. These facilities also allow for the interaction, linkage, and closing of feedback loops between precursor synthesis parameters, thin film processing parameters, and reaction by-product and wastewater parameters.

[0035]

[0036] Another limitation of ex-situ or proximal point-of-use precursor generation is that it cannot provide the critical feedback and information required to ensure that precursor generation and delivery are occurring in a manner that ensures the success of the thin film manufacturing process to achieve the desired thin film target. Conventional ex-situ or proximal point-of-use precursor generation focuses only on evaluating precursor properties and characteristics, such as quality (purity) and flow (amount being delivered to the manufacturing chamber). In contrast, the present invention allows for highly desirable feedback determined by specific film properties measured in real time at the substrate. For example, in-situ sheet resistance and / or thickness measurements can be collected while the manufacturing process is occurring to provide real-time feedback on precursor generation and delivery.

[0036] [Brief explanation of some aspects of the drawing]

[0037] The following detailed description of the preferred embodiments of the invention will be better understood when read in conjunction with the accompanying drawings. For the purpose of illustrating the invention, there are shown in the drawings embodiments which are presently preferred. It being understood, however, that the invention is not limited to the precise arrangements and equipment shown. [Brief description of the drawings]

[0037] [Figure 1] FIG. 2 is a schematic diagram of a precursor synthesis chamber coupled to a thin film processing chamber, according to one embodiment of the present invention. [Diagram 2] FIG. 1 is a schematic diagram of a system including a precursor synthesis chamber that delivers gas phase precursors through a manifold system to a thin film processing chamber in accordance with one embodiment of the present invention. [Diagram 3] FIG. 1 is a schematic diagram of a system including a precursor synthesis chamber that delivers liquid phase precursors to a thin film processing chamber via a manifold system, in accordance with one embodiment of the present invention. [Figure 4] FIG. 1 is a schematic diagram of a system comprising multiple precursor synthesis chambers linked to a single thin film production unit, in accordance with an embodiment of the present invention. [Diagram 5] FIG. 1 is a schematic diagram of a system comprising multiple precursor synthesis chambers in fluid communication with multiple thin film processing chambers, in accordance with one embodiment of the present invention. [Figure 6] FIG. 1 is a schematic diagram of a cluster tool with multiple integrated precursor synthesis chambers and thin film processing chambers, in accordance with one embodiment of the present invention. [Figure 7] 1 is a process schematic of a manufacturing technique involving a flexible substrate in the form of a continuous roll or coil, in accordance with one embodiment of the present invention.

[0038] [Detailed Description of the Invention]

[0045] According to certain embodiments of the present invention, methods and systems are provided to achieve a complete and tightly controlled process and system for fabricating thin film structures by producing and consuming reactive or difficult to handle precursors that utilize real-time in-situ analysis and control, and allow for full coupling and integration of precursor synthesis processes / systems with thin film formation processes / systems. The integrated synthesis, delivery and processing of chemical sources enables embodiments for highly reproducible and reliable thin film fabrication.

[0039]

[0046] Embodiments of the present invention may be applied to any manufacturing process in any industrial setting, including but not limited to the semiconductor (computer chips), aircraft, energy, sensor, medical, biological, chemical and defense industry sectors.

[0040]

[0047] Referring to FIG. 1, a schematic diagram of an integrated precursor synthesis (i.e., production) and thin film deposition system 100 is shown, comprising a first chamber 101 coupled to a second chamber 102, more particularly, a precursor formation chamber 101 coupled under controlled conditions to a thin film processing chamber 102. In one embodiment, the invention thus relates to the integration of one or more precursor formation chambers or modules 101 with one or more process (e.g., deposition, etching, patterning, implantation, etc.) chambers or modules 102. In another embodiment, the invention relates to a process for precursor formation carried out in tandem with a process for thin film formation, etching, implantation or patterning. In another embodiment, the invention relates to a tandem configuration of a precursor formation chamber 101 (or precursor synthesis vessel or precursor synthesis chamber, these terms are used interchangeably herein) in physical contact with a processing chamber 102, where the processing chamber 102 is either a stand-alone processing chamber or part of a collection of processing chambers. The effluent or products of the precursor formation chamber 101 are transported directly to the tandem processing chamber 102 via a tubing or manifold system. Thus, the production of the precursors is controlled not only to optimize the synthesis but also to regulate the efficient deposition of the precursors onto the substrate in the processing chamber(s). The present invention enables the reliable fabrication of both new thin film structures and expands the conditions under which traditional thin films can be fabricated.

[0041]

[0048] The precursor formation chamber 101 may have one or more inlets necessary to perform its function, including an inlet for raw materials 104, utilities 109 such as power, and electronic monitoring and control equipment for managing and controlling the operation of the precursor formation chamber 101. More specifically, the integrated system 100 further comprises a raw material supply 104 and an associated feeding system that delivers the precursor base or raw materials in a controlled manner (utilizing various control utilities 109, e.g., power, vacuum, heat, cooling, radiation, etc.) to the precursor formation chamber 101 via a first conduit 105 (i.e., raw material supply conduit) and a raw material inlet 106 for synthesis of the precursor in the precursor formation chamber 101. Thus, the precursor formation chamber 101 is not merely a storage vessel for precursors, but rather a reactor in which precursor materials are produced from raw materials fed thereto.

[0042]

[0049] The precursor formation chamber 101 further comprises a precursor outlet 107 through which the generated precursor is supplied or transported from the precursor synthesis chamber 101 to the processing chamber 102. More specifically, the precursor leaves the precursor formation chamber 101 through the outlet 107 and is then transported in a precise controlled manner (with the aid of various control utilities 109, e.g., electrical power) in solid, liquid or vapor form via a second tube 108 (i.e., precursor transport tube) to the processing chamber 102, where the synthesized precursor is processed to grow, etch, implant or pattern a thin film from the precursor. Thus, the precursor formation chamber 101 and the processing chamber 102 are connected and in direct communication with each other.

[0043]

[0050] In another embodiment (not shown), instead of separate and distinct chambers separated by conduits, the precursor formation chamber and the processing chamber may constitute different chambers, sections or regions of a single tank, and may be separated from one another in the tank by a shared wall or partition. In such an embodiment, the wall or partition preferably comprises openings with valves and controls to selectively isolate the chambers from one another or to allow the flow of precursors from the precursor synthesis chamber to the processing chamber. Thus, despite the absence of precursor transport conduits, the precursor synthesis chamber and the processing chamber are still considered to be connected and in direct communication with one another.

[0044]

[0051] In one embodiment, the precursor formation chamber 101 is preferably a precursor synthesis chamber, hereinafter alternatively referred to as a precursor synthesis chamber.

[0045]

[0052] In one embodiment, the raw material supply conduit 105, precursor transport conduit 108, precursor synthesis chamber 101 and / or processing chamber 102 are equipped with one or more valve assemblies 103 and electronic sensors (not shown) for real-time in-situ monitoring and detection of raw material delivery, precursor delivery, thin film processing and by-product processing endpoints. For example, such valves 103 and sensors allow precursors to flow from the precursor synthesis chamber 101 to the thin film processing chamber 102 in a reliable, controlled and consistent manner. The valve system also effectively isolates the precursor synthesis chamber 101 from the processing chamber 102. More specifically, in one embodiment, the valve system includes one or more valves 103 using devices such as O-rings or metal gaskets to effectively separate the environments of the two chambers 101, 102.

[0046]

[0053] The precursor synthesis chamber 101 may also have facilities, systems, or manifolds 110 for evacuating materials that are unnecessary or even harmful to the precursor synthesis. Such materials may include fluids used to purge the chamber 101, synthesis reaction by-products that may be generated during start-up of the chamber 101 or as a result of a process disturbance, and / or manufactured precursors having qualities outside the control limits or thin film fabrication or modification needs.

[0047]

[0054] The precursor synthesis chamber 101 may also be equipped with in-situ and ex-situ monitoring and detection techniques, spectroscopy and spectrometry to monitor and control various parameters of the precursor synthesis process. Such parameters may include, but are not limited to, temperature, pressure, flow rates of raw materials and precursors, and all operating conditions of the chemical synthesis production itself. Electronic sensors and in-situ and ex-situ monitoring and detection techniques, spectroscopy and spectrometry also enable endpoint real-time in-situ monitoring and detection. These facilities also enable interactions, linkages and closed feedback loops between precursor synthesis parameters, thin film processing parameters, and reaction by-product and wastewater parameters. More specifically, the present invention enables closed-loop precursor synthesis and thin film processing by controlling and managing the link between precursor production / synthesis, precursor consumption and thin film processing using in-situ and / or ex-situ built-in sensors. In some embodiments, the sensors include, but are not limited to, optical, acoustic, electrical (e.g., sheet resistance), electronic, magnetic, mechanical, electromechanical and electromagnetic sensors.

[0048]

[0055] Further, the present invention thus ensures accurate and controlled management of precursor characteristics, such as feed rates to the production and processing chamber 102; thin film formation characteristics, such as thickness and composition; and reaction by-products and processing chamber effluent characteristics, such as chemical composition and flow rate. In some embodiments, monitoring and detection techniques include, but are not limited to, ellipsometry and mass spectrometry, as well as infrared, near infrared, optical and ultraviolet spectroscopy. In one embodiment, the difference can be incorporated into an algorithm for controlling the rate of precursor production in the precursor formation chamber 101 and / or transport and delivery to the thin film fabrication chamber 102 to perform a relative evaluation of the amount or concentration of precursor exiting the thin film processing or formation chamber 102 versus the amount or concentration of precursor exiting the precursor synthesis chamber 101. In a preferred embodiment, the amount of precursor production in the precursor formation / synthesis chamber 101 is controlled by an algorithm that takes into account thin film properties, such as thickness or sheet resistance by ellipsometry.

[0049]

[0056] The precursor synthesis and thin film deposition processes can be performed in tandem or simultaneously, with feedback from one of the chambers 101, 102 controlling the operation of the other chamber 101, 102. For example, thin film formation in the second chamber 102 (e.g., processing chamber or deposition chamber, these terms are used interchangeably herein) is monitored, preferably continuously monitored, and feedback is communicated to the precursor synthesis chamber 101 to control the precursor formation / synthesis. In the simplest case, if there is no precursor demand in the deposition chamber 102, the precursor production in the precursor synthesis chamber 101 is stopped. That is, the precursor production is coupled with the demand for thin film formation and coincides with the introduction of co-reactant entering the deposition chamber 102. Thus, there is a two-way communication between the precursor synthesis chamber 101 and the deposition chamber 102, and the operation of both chambers 101, 102 is controlled by a controller based on the monitored parameters of each chamber 101, 102.

[0050]

[0057] In some embodiments, the fabrication technique is one of chemical vapor deposition (CVD), atomic layer deposition (ALD), liquid plating, etching (including atomic layer etching, as well as partial and full material removal processes), or patterning (i.e., forming a predetermined structure in a previously deposited layer, e.g., a transistor pattern in a silicon substrate).

[0051]

[0058] In some embodiments, the controlled environment in which the precursor synthesis chamber 101 is coupled to the processing chamber 102 is one of vacuum, inert gas, hydrogen, reactive gas, or a combination of such gases.

[0052]

[0059] In some embodiments, the process chamber 102 is a batch tool where a manufacturing technique is applied simultaneously to multiple wafers in a single manufacturing apparatus, while in other embodiments, the process chamber 102 is a stand-alone tool where a manufacturing technique is applied to a single wafer in an individual apparatus.

[0053]

[0060] In some embodiments, the precursor molecules are volatilized or evaporated and transported into the process chamber 102 using their own vapor pressure, while in other embodiments, the precursor molecules are transported using an inert or reactive carrier gas. The precursors can be in liquid, solid or gas form.

[0054]

[0061] In some embodiments, the precursor synthesis chamber contains a method for separating by-product chemicals, for example, selective adsorption beds, such as activated carbon, molecular sieves, or metal-organic frameworks that remove the by-products from the vapor transport stream.

[0055]

[0062] In a particularly preferred embodiment, the invention relates to the integrated tandem production and consumption of toxic materials in a precursor synthesis reactor coupled to a metal deposition chamber. For example, nickel carbonyl is a precursor to nickel thin films and is representative of metallization processes that can be performed in a tandem precursor production cluster tool.

[0056]

[0063] Nickel carbonyl is highly toxic and carcinogenic at ppm levels. Depending on local regulations, the transport and storage of nickel carbonyl is either highly regulated or completely prohibited. Furthermore, nickel carbonyl has limited stability and slowly decomposes even at room temperature to form nickel and carbon monoxide. In one embodiment of the invention, bulk metallic nickel is loaded into the precursor synthesis chamber 101. The preferred form of nickel is a partially sintered nickel monolith that retains its porosity. The chamber 101 is sealed and then appropriately purged and evacuated to remove absorbed and residual gases. The nickel monolith is then heated to a temperature between 80°C and 120°C. At this stage, a flow of carbon monoxide begins to flow due to the opening of the valve of the precursor delivery tube 108, which allows flow from the precursor synthesis chamber 101 to the deposition chamber 102. The connection to the deposition chamber 102 can include, for example, a near-infrared detector system, which can detect and quantify the presence of the precursor (i.e., nickel carbonyl) in the deposition chamber 102.

[0057]

[0064] In the deposition chamber 102, a substrate (not shown) is heated to a temperature in the range of 180°C to 250°C. Nickel carbonyl decomposes at the substrate to form a very pure nickel film. Data from the nickel carbonyl observation window and deposition chamber controls are utilized to adjust (preferably by a controller) the temperature of the sintered nickel monolith and / or the carbon monoxide flow rate. The ratio of excess carbon monoxide entering and / or leaving the deposition chamber 102 can be measured by the process control and adjusted to achieve an optimal deposition rate and optimal film properties.

[0058]

[0065] Under similar conditions, a cobalt film can be formed.

[0059]

[0066] Another embodiment of the present invention relates to the formation of silicon nitride at low temperatures utilizing hydrazoic acid. Hydrazoic acid, also known as hydrogen azide, can decompose explosively when stored in bulk and has a toxicity comparable to cyanide. Hydrazoic acid decomposes at relatively low temperatures to form radical nitrogen products, including nitrenes, which can insert into Si-H bonds. Silicon nitride films can be formed in the deposition chamber 102 by nitridation of amorphous silicon hydride or by reacting both hydrazoic acid and silanes (or higher polysilanes) with the substrate in the deposition chamber 102. In the present invention, for example, hydrazoic acid is formed in the tandem deposition chamber 102 as a low concentration vapor with a suitable inert carrier gas. One preferred method of generating hydrazoic acid is to have a high boiling hydroxyl liquid in the precursor synthesis chamber 101 with a bottom gas inlet below the liquid level and a gas outlet above the liquid. Trimethylsilyl azide is entrained in a gas stream, which enters a hydroxyl liquid heated to a temperature of 40-65°C. The trimethylsilyl azide reacts with the hydroxyl liquid to form, for example, non-hazardous trimethylsilylstearyl alcohol, while producing hydrazoic acid. The hydrazoic acid entrained in a carrier gas then enters the deposition chamber 102, where it can react with the amorphous hydrogenated silicon substrate at 325°-500° to form silicon nitride. As in the previous embodiment, the rate of production of hydrazoic acid in the precursor synthesis chamber 101 is matched by a suitable control mechanism to its consumption rate in the deposition chamber 102. An alternative method of producing hydrazoic acid is the continuous production of materials at high temperatures by thermally driven reverse Diels Alder reaction of compounds such as 4,7-methano-3a,4,5,6,7,7a-hexahydrobenzotriazole.

[0060]

[0067] Additionally, it will be understood by those skilled in the art that one or more of the above example steps utilizing nickel carbonyl or hydrazoic acid may be used with any known precursor and system / method of the present invention.

[0061]

[0068] The present invention also has great utility when the time scale of stability of the precursor reactants is fairly short and their utilization is limited only by this factor and not by toxicity. For example, graphene films are difficult to grow and modify. One such method can be to form benzine. The stability of benzine at temperatures above 100° C. in moderate concentrations is on the order of a few seconds. Benzine can be formed from intermediates such as 2-(trimethylsilyl)phenyl trifluoromethanesulfonate. In this embodiment, an inert gas mixed with the compound passes through a high temperature heating block in the tandem precursor generation chamber 101 to form benzine and the by-product trimethylsilyl trifluoromethanesulfonate. While the by-product is not reactive with graphene, benzine reacts with graphene, thereby extending the polycyclic structure.

[0062]

[0069] In another embodiment, the synthesis of precursors can be produced by consumption linked to electrochemical synthesis. Examples of toxic precursors that can be produced include arsine, phosphine, germane and hydrogen selenide. Relatively unstable precursors, such as stannanes, can also be produced in concert with consumption.

[0063]

[0070] Another embodiment of thermal stability is the formation of silicon nitride. t-Butylaminochlorosilane has a half-life in the range of several days at room temperature. However, t-Butylaminochlorosilane is stable for several months at temperatures of -40°C. In this case, the tandem precursor chamber 101 is formed with a cryocontainer capable of dispensing liquid into a flowing carrier gas stream at a temperature suitable for transport. Substrate temperatures of 300°C to 350°C and a co-reactant of ammonia allow the formation of SiN films.

[0064]

[0071] Yet another embodiment of the advantages of deposition and tandem precursor generation is the low temperature deposition of silicon nitride from monosilylamine. At gas concentrations above about 2%, monosilylamine reacts with itself to form disilylamine and ultimately trisilylamine. Monosilylamine can form nitrogen-enriched amorphous silicon hydride films at temperatures in the 200° C. range, but currently there is no practical method to store and utilize monosilylamine. In this example, the tandem precursor chamber 101 is a plug flow reactor with a series of static flow mixers (not shown). Ammonia and monochlorosilane are introduced as separate gas streams in a suitable inert carrier gas. The flow rates and concentrations are adjusted to optimize the production of monosilylamine, but also to minimize unreacted monochlorosilane and disilylamine and trisilylamine decomposition products. In this embodiment of the invention, the gas stream is first bypassed from the deposition chamber 102 and analyzed by mass spectrometry (RGA), and is allowed to enter the deposition chamber 102 only if the gas stream is within control parameters.

[0065]

[0072] In another embodiment, the precursor synthesis chamber is for the controlled synthesis of heavy halides of metals. A quartz tube filled with granular or reactive metals, such as silicon, titanium or tantalum, is placed in an inductively heated furnace. The tube is configured to allow vapor of the heavy halide, bromine or iodine, to pass through the granular mass. Inductive heating of the metal to a temperature that allows for reaction with the halogen is pulsed in coordination with the ALD consumption pulse in the deposition chamber. In a specific embodiment, polycrystalline silicon grains are loaded into the quartz tube, and iodine vapor heated to over 200° C. enters the silicon loaded bed. In coordination with the 1 minute ALD pulse time, the temperature of the silicon metal is inductively heated to 650° C.-1000° C. in 1 minute, and the amount of iodine in the vapor body is utilized to control the rate of formation of silicon tetraiodide, which is then controlled to match the requirements of the ALD pulse in the film formation chamber. The induction heating pulse controls the rate and duration of silicon tetraiodide formation, while the amount of halogen vapor controls the amount of silicon tetraiodide formed. The transport of silicon tetraiodide passes through a heat exchange section where the temperature of the silicon tetraiodide vapor is controlled, preferably between 125°C and 350°C, to avoid the formation of solid silicon tetraiodide. In the film formation chamber, the pulse from the silicon tetraiodide chamber is modified by an inert gas purge, followed by an ammonia purge, followed by an inert gas purge. In doing so, a silicon nitride film is formed. Similarly, other metal halides can be formed by replacing the metal. Depending on the conditions in the film formation chamber and the reactants exchanged, nitride, oxide and metal (zero valent) films, among others, can be formed.

[0066]

[0073] In another embodiment, two reactant gases and optionally one carrier gas are introduced into the precursor synthesis chamber 101, the waste water of which proceeds to the thin film processing chamber 102. The precursor synthesis chamber comprises a series of chambers capable of mixing, potentially including a static mixer, and which may be equipped with heating or cooling mechanisms. Under suitable pressure, the carrier gas and one of the reactant gases are introduced into the first stage of the static mixing chamber, controlled by a mass flow meter. Before the next static mixing element, the second reactant gas is introduced into the synthesis stream, also under the control of a mass flow meter. If the reaction is highly exothermic, cooling may be necessary in the second stage. However, at least both stages are under thermal control, either by a jacket with a circulating liquid or another known thermal control method. Leaving the static mixing element, the product stream is analyzed by residual gas analysis (RGA), mass spectrometry, NIR (near infrared) or UV analysis.

[0067]

[0074] Through appropriate valves, the flow is first diverted to the reduction process. However, as soon as the proper ratio of precursors is achieved, the flow passage goes directly to the processing chamber 102 where the utilization of the active components is monitored. Once the film processing is complete, as measured by ellipsometry, sheet resistance or other suitable parameters, the introduction of reactant gases into the precursor synthesis chamber 101 is stopped by a control loop that closes a valve placed before the mass flow meter. Preferably, a by-product removal stage is included in the process stream as part of the precursor synthesis chamber 101. The by-product removal element may include, for example, a cryogenic trap, an adsorption step or a separate chemical reaction process specific to the by-product.

[0068]

[0075] In another embodiment, particularly when monosilylamine is utilized for silicon nitride deposition, monosilylamine and ammonia reactant (which may also act as a carrier gas) or alternatively nitrogen (which may act as a separate carrier gas) are introduced into the first stage of the static mixer. Leaving the first stage as a homogeneous mixture, monochlorosilane is introduced into the flow before the second static mixing element. A mass flow meter controls the amount and concentration of monosilylamine formed in the second static mixing element by utilizing analytical information obtained by the RGA. Either before or after the analysis, the by-product ammonium chloride can be removed by passing the process flow through a packed bed of pelleted charcoal, preferably cooled to a temperature below -10°C. However, in some cases, this step is not necessary, as ammonium chloride can pass directly through the thin film processing chamber 102 without affecting the deposition process.

[0069]

[0076] In another embodiment, two interconnected subchambers behave as one precursor synthesis chamber 101. The purpose of the first subchamber is to entrain a liquid reactant in a gas stream that carries the reactant under control to the second subchamber, where it reacts with a relatively non-volatile material, thus forming a volatile precursor that proceeds under controlled conditions to the thin film process chamber 102. The by-products are retained in the second subchamber. It should be noted that while the reactant volume of the first subchamber is depleted, the second subchamber is not necessarily depleted since it contains by-products. The first subchamber can be considered similar to what is called a bubbler in the art, where a volatile liquid is charged to the container and a dip tube allows the introduction of gas below the surface of the liquid reactant, and as the gas progresses through the liquid phase, the liquid is entrained in the vapor stream that exits the chamber above the level of the liquid. The amount of entrained reactant is controlled by the velocity of the carrier gas passing through the bubbler and the temperature of the liquid in the subchamber. The entrained reactants then pass through a dip tube to a second sub-chamber that functions as a reactor. The reaction chamber is comprised of a dip tube, typically heated with stirring, and equipped with a vapor phase outlet connected to the thin film processing chamber 102. A second non-volatile reactant is introduced into the reaction chamber. In a preferred embodiment, the contact time with the entrained reactants is sufficient to ensure that the volatile reactants are completely consumed, and that the airflow leaving the reaction chamber contains carrier gas and volatile precursors for thin film synthesis.

[0070]

[0077] As shown here, the input reactants and by-products, excluding any entrained mass in the carrier gas, are the only materials leaving the precursor synthesis chamber 101. However, an obvious extension of this concept is to replenish and replace the reactive materials and by-products of the precursor synthesis chamber 101 in a controlled process.

[0071]

[0078] One such embodiment contains hydrazoic acid (hydrogen azide) and trimethylsilyl azide charged into a bubbler. The second sub-chamber is charged with stearyl alcohol (octadecanol), heated to a temperature above 60° C. (above the melting point of stearyl alcohol) and stirred. The nitrogen flow entrains the trimethylsilyl azide which reacts with the stearyl alcohol to form the volatile precursor hydrazoic acid, which is entrained in the nitrogen carrier gas and directed to the thin film processing chamber 102. The by-product stearyloxytrimethylsilane does not volatilize and remains in the reaction chamber.

[0072]

[0079] It should be understood that the above discussion regarding FIG. 1 and the associated preferred embodiments applies equally to FIGS. 2-7, the detailed discussion of which is set forth below.

[0073]

[0080] Referring to FIG. 2, a schematic diagram of a system is shown comprising a precursor synthesis chamber 201 connected to a thin film processing chamber 202 via a manifold system 206 suitably equipped to supply gas phase precursors and deliver gaseous, liquid or solid precursors in gaseous or vapor form. The raw material or base material(s) for the precursors are provided from a raw material source (not shown). The manifold system 206 may comprise an electronic mass flow meter or a solid or liquid delivery system. The manifold system 206 may also include further devices and controls such as a purge gas system 203 and corresponding venting system 205 for purging and / or evacuating the tubes or pipes 207 connecting the precursor synthesis chamber 201 and the thin film processing chamber 202.

[0074]

[0081] In one embodiment, the manifold system 206 may also include various mechanisms and controls, generally shown as 204, for conditioning the gases, for example, by including electronic stabilizers to eliminate variations in precursor feed, filtration of particulate matter, or adsorption of impurities that may be generated in the transfer from the precursor synthesis chamber 201 to the processing chamber 202. The transfer process may also include additional mechanisms for monitoring and control of the transfer, for example, temperature, pressure, and flow rate.

[0075]

[0082] Referring to Figure 3, there is shown a schematic diagram of a precursor synthesis chamber 301 supplying or delivering liquid phase precursors to a thin film processing chamber 302 via a manifold system 306 suitably equipped to deliver liquid phase precursors. The precursors may be in solid or liquid form, supplied from a raw material source (not shown), with solid precursors being subjected to a liquefaction or melting process or dissolved in a suitable liquid or solvent prior to delivery to the thin film processing chamber 302. Further equipment and controls of the manifold system 306 include a solvent system 303 for cleaning or removing residual precursors from the line (i.e., transfer tube) 307, a purge system 304 for removing residual solvent from the transfer tube 307, a corresponding vent system 308 for purging and / or evacuating the transfer tube 307, and a solvent waste component 309. Various instruments and controls 305 may also be included for management and control of the delivery of the proper amount of precursors at the proper purity to the processing chamber 302. Such equipment may include instruments for monitoring temperature, pressure and flow, treating precursors to remove particulate matter or other impurities, or vaporizing liquid precursors immediately prior to introduction into the thin film process chamber 302.

[0076]

[0083] 4, there is shown a schematic diagram of an embodiment of a system comprising multiple precursor synthesis chambers 404a, 404b, 404c coupled in a controlled environment to a single thin film fabrication station or processing chamber 403. Multiple precursors are synthesized in the precursor synthesis chambers 404a-404c and then simultaneously or sequentially transported to the processing chamber 403 where they are consumed in a fabrication (e.g., deposition) technique. The precursor synthesis chambers 404 may be configured with respective gas or liquid delivery systems or other subsystems as may be required for the overall operation of the system, as described above with respect to FIGS. 1-3.

[0077]

[0084] The precursor synthesis chambers 404a-404c may be arranged in various configurations. For example, some or all of the precursor synthesis chambers 404a-404c may be arranged in parallel (i.e., see chambers 404a and 404b in FIG. 4) such that single or multiple precursors are simultaneously delivered from each chamber 404a-404c to the deposition chamber 403. Alternatively, some or all of the precursor synthesis chambers 404a-404c may be arranged in a tandem or serial arrangement (i.e., see chambers 404b and 404c in FIG. 4) such that single or multiple precursors are delivered in sequence from one synthesis chamber (i.e., chamber 404c in FIG. 4) to a second synthesis chamber (i.e., chamber 404b in FIG. 4) and then the resulting mixture of precursors is delivered to the processing chamber 403. The configuration may also include any other arrangement that may be configured by a combination of parallel and tandem arrangements. Additionally, the parallel arrangement of chambers can be operated sequentially, simultaneously, or in any other combination as needed to produce the desired effect in the thin film process chamber 403. A wafer handling system 401 is also provided for moving substrate wafers between the storage cassette 402 and the thin film process chamber 403.

[0078]

[0085] Referring to FIG. 5, a schematic diagram of an embodiment of a system is shown that includes multiple precursor synthesis chambers (PSC) 504a, 504b in fluid communication with multiple thin film processing chambers (TPC) 505a, 505b. Each of the precursor synthesis chambers 504a, 504b includes a gas or liquid delivery system as described above with respect to FIGS. 1-3. The wafer handling system 501 of FIG. 5 includes a mechanism 502, in this example a robotic arm, for transporting substrate wafers through a storage cassette 503, the various thin film processing chambers 505a, 505b, and one or more metrology (M) chambers 506 that are used to monitor characteristics of each substrate wafer as it progresses through the processing chambers 505a, 505b. The precursor synthesis chambers 504a, 504b are configured to produce the same precursor, different precursors, or any combination thereof. The operating mode of the system is established such that a substrate wafer may visit only one of the thin film processing chambers 505a, 505b or any combination of the thin film processing chambers 505a, 505b as may be required for overall process optimization or fabrication of single or multi-layer films or structures. A fabrication process may include a single processing step, e.g., film deposition, etching, ion implantation or patterning, or may consist of a combination of processing steps, e.g., a full set or a subset of deposition, etching, ion implantation and patterning processes.

[0079]

[0086] Referring to FIG. 6, an embodiment of a cluster tool is shown that includes multiple integrated precursor synthesis chambers or generators 603a, 603b, 603c, 603d, 603e and thin film processing chambers 602a, 602b, 602c, 602d, 602e arranged around a central automated handling unit with fixed precursor inlets feeding each processing chamber 602a, 602b, 602c, 602d, 602e. Wastewater from the precursor synthesis chambers 603a, 603b, 603c, 603d, 603e can be directed to a safe location (e.g., a scrubber) 609 away from the thin film process chambers 602a, 602b, 602c, 602d, 602e until the thin film process chambers 602a, 602b, 602c, 602d, 602e are fully conditioned and ready for the introduction of precursors, and it has been determined that the precursors exhibit the specifications and characteristics required by the thin film manufacturing process.

[0080]

[0087] Substrate wafers are transported from the storage cassette 601 via a robotic arm 608 or other automated system to the thin film processing chambers 602a, 602b, 602c, 602d, 602e (or other chambers that may be included for overall utility of the cluster tool). The precursor synthesis chambers 603a, 603b, 603c, 603d, 603e are each connected to a raw material supply via tubing (not shown) as described above with respect to FIG. 1, and may be configured to control precursor synthesis by advanced techniques to maintain, for example, a particular precursor purity and flow rate to the thin film process chambers 602a, 602b, 602c, 602d, 602e.

[0081]

[0088] With reference to Figure 6, while such a control loop concept is provided for one precursor synthesis chamber 603c, it will be understood that such a control loop may be applied to any one or more of the other precursor synthesis chambers 603a, 603b, 603d, 603e, either in the same manner or with protocols modified to meet various control objectives for different precursor or thin film manufacturing processes. Specifically, in the control loop shown in Figure 6, one or more signals are read from one or more instruments 604, 605 in the thin film process chamber 602c, the precursor synthesis chamber 603c, or both. For example, the thin film process chamber 602c may include a process chamber sensor 604, and the precursor synthesis chamber 603c may include a chemical generator sensor 605. Signals from these sensors 604, 605 are processed through function blocks 606 to provide inputs to a controller 607 (more specifically, a chemical generator controller) that adjusts the operation of the precursor synthesis chamber 603c to meet the manufacturing objectives. Such instruments may include electronic sensors for endpoint real-time in-situ monitoring and detection and / or in-situ and ex-situ monitoring and detection techniques, spectroscopy and spectrometry to monitor and control various parameters of the precursor synthesis process.

[0082]

[0089] In some embodiments, the system comprises one or more interconnected fabrication or processing chambers set up in a sequential or serial manner, where the fabrication techniques are applied to successive substrates, which are moved sequentially from one chamber to the next, where they are subjected to one or more fabrication techniques. An example of such an embodiment is roll-to-roll coating of a continuous film onto a flexible substrate. In one such embodiment, one or more precursor synthesis modules or chambers are coupled to the fabrication or processing chambers, where one or more precursors are delivered to the flexible substrate or sprayed onto the flexible substrate in either vapor or liquid form, where they are decomposed or processed to produce a film on the flexible substrate.

[0083]

[0090] More specifically, referring to FIG. 7, there is shown a schematic diagram of the application of manufacturing techniques to flexible substrates in the form of continuous rolls or coils (e.g., ribbons, rolls or spools) rather than in the form of separate or discrete units (e.g., wafers). A stock roll 701 of flexible substrate is unwound or unfolded and fed in a controlled manner into one or more interconnected fabrication or processing chambers 703a, 703b arranged sequentially or in series and exposed to a sequence of one or more manufacturing techniques designed to produce a target thin film structure in the flexible substrate. The manufacturing techniques may include the same processing steps, e.g., film deposition, etching, ion implantation or patterning. Alternatively, the manufacturing techniques may include a combination of processing steps, e.g., a full set or subset of deposition, etching, ion implantation and patterning processes, each in its own processing or fabrication chamber.

[0084]

[0091] The fabrication techniques are preferably isolated from each other and each enclosed within its own processing chamber 703a, 703b. One or more intervening chambers 704 (e.g. metrology chambers) are preferably provided to facilitate isolation and / or process control. Each process chamber 703a, 703b is associated with one or more precursor synthesis chambers 705a, 705b. The precursor synthesis chambers 705a, 705b can all deliver the same precursors, either in vapor or liquid form, to every individual fabrication or processing chamber 703a, 703b, where the precursors are fully or partially decomposed or processed or consumed to produce a film on the flexible substrate. Alternatively, each precursor synthesis chamber 705a, 705b can deliver different precursors, either in vapor or liquid form, to the corresponding fabrication or processing chamber 703a, 703b, where each precursor is fully or partially decomposed or processed or consumed to produce a layer of a multi-layer film on the flexible substrate.

[0085]

[0092] A control manifold with measurement instrumentation 707a, 707b, and 708 and conversion process models 709a, 709b in communication with process controllers 706a, 706b via lines or tubes 711a, 711b is incorporated to provide feedback and feedforward control to the individual precursor synthesis chambers 705a, 705 to match given pre-set processing set points 710a, 710b. The resulting processed flexible substrate is unwound on an end roll 702. In one embodiment, the instruments 707a, 707b are in-situ sensors and the instrument 708 is an ex-situ sensor. In one embodiment, the process controllers 706a, 706b are chemical source (i.e., precursor) controllers and the conversion process models 709a, 709b are signal converters.

[0086]

[0093] In some embodiments, one or more precursors are decomposed or processed on a flexible substrate using sol-gel or plating techniques to form a layer or film. In other embodiments, the precursors are decomposed or processed on a flexible substrate using CVD or ALD techniques. In other embodiments, the resulting film comprises a single uniform layer or multiple layers depending on the number of different precursors used.

[0087]

[0094] It will be appreciated by those skilled in the art that changes may be made to the above-described embodiments without departing from the broad inventive concept thereof. It is understood therefore that the invention is not limited to the particular embodiments disclosed, but that the invention is intended to encompass modifications within the spirit and scope of the invention as defined in the appended claims.

Claims

1. 1. An integrated system for the synthesis of film-forming precursors, consumption of said precursors and formation of thin films on a substrate, comprising: The system further comprises: a raw material source containing at least one raw material; at least one precursor synthesis chamber having an inlet and an outlet, the inlet of the at least one precursor synthesis chamber being in communication with the raw material supply source, the at least one raw material being supplied to the at least one precursor synthesis chamber via the inlet, where the raw materials are reacted to synthesize a precursor; a thin film processing chamber coupled to said at least one precursor synthesis chamber, said thin film processing chamber comprising an inlet in direct communication with and coupled to said outlet of said at least one precursor synthesis chamber for transporting said precursor directly from said at least one precursor synthesis chamber to said thin film processing chamber in a controlled manner to consume said precursor in said thin film processing chamber to form said thin film on said substrate; a monitoring system configured to perform real-time monitoring and detection of all three process components: thin film processing parameters in the thin film processing chamber; precursor synthesis in the at least one precursor synthesis chamber; and precursor consumption in the thin film processing chamber; and (ii) a controller configured to receive and process data from the monitoring system relating to optimizing precursor synthesis by reaction of the at least one raw material supplied to the at least one precursor synthesis chamber, and to simultaneously control precursor consumption rates and thin film formation rates based on said data to ensure that precursor consumption rates and thin film formation rates are synchronized with precursor synthesis rates.

2. 10. The integrated system of claim 1, wherein the controller is configured to compare the amount or concentration of the precursor entering the thin film processing chamber with the amount or concentration of the precursor exiting the precursor synthesis chamber, calculate a difference, and utilize the difference as part of an algorithm for controlling the precursor synthesis rate in the precursor synthesis chamber.

3. 2. The integrated system of claim 1, wherein the system is a feedback loop system comprising the precursor synthesis chamber and the thin film processing chamber directly coupled thereto, without any additional chambers, vessels, or reactors for depositing, storing, or further processing the precursors, and the monitoring system and the controller control and manage the communication between the precursor synthesis in the precursor synthesis chamber and the precursor consumption to form the thin film formation in the thin film processing chamber.

4. The integrated system of claim 1 , wherein the controller adjusts the precursor synthesis rate based on the rate of precursor consumption.

5. 2. The integrated system of claim 1, wherein the monitoring system comprises at least one of in-situ monitoring and detection techniques, ex-situ monitoring and detection techniques, spectroscopy, and spectrometry for monitoring at least one parameter selected from the group consisting of process parameters of the precursor synthesis chamber, process parameters of the thin film processing chamber, reaction by-product and wastewater parameters, and at least one property of the thin film.

6. 6. The integrated system of claim 5, wherein the at least one parameter is selected from the group consisting of temperature, pressure, flow rate of one or more materials, flow rate of the precursor, and reaction conditions of precursor synthesis.

7. 6. The integrated system of claim 5, wherein the in-situ and ex-situ monitoring and detection techniques include at least one technique selected from the group consisting of ellipsometry, mass spectrometry, infrared spectroscopy, near infrared spectroscopy, optical spectroscopy and ultraviolet spectroscopy.

8. 2. The integrated system of claim 1, wherein the monitoring system comprises at least one in-situ embedded sensor and / or at least one ex-situ embedded sensor for real-time monitoring and detection of at least one processing parameter of the system and / or at least one property of the thin film.

9. 9. The integrated system of claim 8, wherein the at least one in-situ embedded sensor and / or the at least one ex-situ embedded sensor is selected from the group consisting of optical sensors, acoustic sensors, electrical sensors, electronic sensors, magnetic sensors, mechanical sensors, electromechanical sensors and electromagnetic sensors.

10. 9. The integrated system of claim 8, wherein the at least one parameter is selected from the group consisting of temperature, pressure, flow rate of one or more materials, flow rate of the precursor, and reaction conditions of precursor synthesis.

11. 10. The integrated system of claim 1, wherein the precursor synthesis chamber and the thin film processing chamber are separate and distinct chambers, and the internal environments of the precursor synthesis chamber and the thin film processing chamber are isolated from each other by a valve assembly.

12. 10. The integrated system of claim 1, wherein the precursor synthesis chamber comprises a vent outlet for exhausting purge fluids or reaction by-products.

13. 10. The integrated system of claim 1, further comprising a manifold system connecting the outlet of the precursor synthesis chamber with the inlet of the thin film processing chamber for flow of vapor phase precursors.

14. 14. The integrated system of claim 13, further comprising a purge gas system and a vent system for purging and evacuating tubes of the manifold system.

15. 10. The integrated system of claim 1, further comprising a manifold system connecting the outlet of the precursor synthesis chamber with the inlet of the thin film processing chamber for flow of liquid phase precursors.

16. 16. The integrated system of claim 15, further comprising a cleaning system configured to supply a solvent solution to the tubes of the manifold system to clean the tubes, and a purge system for removing residual solvent solution from the tubes of the manifold system.

17. 13. The integrated system of claim 1 comprising multiple precursor synthesis chambers coupled with a single thin film processing chamber.

18. 20. The integrated system of claim 17, wherein at least two of the plurality of precursor synthesis chambers are configured in a parallel arrangement to deliver precursors from each precursor synthesis chamber of the parallel arrangement simultaneously to the single thin film processing chamber.

19. 20. The integrated system of claim 17, wherein at least two of the plurality of precursor synthesis chambers are configured in a series or tandem arrangement to deliver precursors from an upstream precursor synthesis chamber to a downstream precursor synthesis chamber to form a mixture of precursors and subsequently deliver said mixture of precursors from the downstream precursor synthesis chamber to the single thin film processing chamber without any additional chambers, vessels, or reactors for depositing, storing, or further processing any of the precursors or their mixtures.

20. 10. The integrated system of claim 1 comprising a plurality of precursor synthesis chambers coupled to a plurality of thin film processing chambers.

21. 21. The integrated system of claim 20, further comprising a storage cassette for storing at least one substrate, a plurality of metrology chambers for monitoring at least one characteristic of the substrate, and a transport mechanism for transporting the substrate through the storage cassette, the plurality of thin film processing chambers, and the plurality of metrology chambers.

22. 21. The integrated system of claim 20, further comprising a cluster tool integrated with said plurality of precursor synthesis chambers and said plurality of thin film processing chambers.

23. 21. The integrated system of claim 20, wherein each precursor synthesis chamber is coupled to a corresponding thin film processing chamber for delivering the same precursor in vapor or liquid form to said corresponding thin film processing chamber.

24. 21. The integrated system of claim 20, wherein each precursor synthesis chamber is coupled to a corresponding thin film processing chamber for delivering a different precursor in vapor or liquid form to said corresponding thin film processing chamber.

25. 21. The integrated system of claim 20, wherein the substrate is a flexible substrate in the form of a continuous roll or coil, such as a ribbon, roll, tape, or spool.

26. 26. The integrated system of claim 25, wherein the flexible substrate comprises an unwound or unfolded stock roll that is fed in a controlled manner into one or more of the plurality of interconnected thin film processing chambers.

27. 27. The integrated system of claim 26, wherein the interconnected thin film processing chambers apply the same manufacturing technique to the substrates.

28. 27. The integrated system of claim 26, wherein each of the interconnected thin film processing chambers applies a different manufacturing technique to the substrate.

29. The integrated system of claim 1 , wherein the precursor is selected from a group of chemicals that are unstable at room temperature.

30. 10. The integrated system of claim 1, wherein the precursor is one of nickel carbonyl and hydrazoic acid.

31. The integrated system of claim 1 , wherein the thin film processing chamber is one of a batch tool, a stand-alone tool, and a cluster tool.

32. 1. An integrated method for the synthesis of a film-forming precursor, consumption of said precursor, and formation of a thin film on a substrate, comprising: providing a raw material supply source containing at least one raw material at a first location; providing said at least one raw material from said raw material source to a precursor synthesis chamber at said first location; reacting the at least one raw material in the precursor synthesis chamber at the first location to form a precursor; at said first location, delivering in a controlled manner said precursor from said precursor synthesis chamber to a thin film processing chamber in tandem with and directly coupled to said precursor synthesis chamber, without any additional chambers, vessels or reactors for depositing, storing or further processing said precursor; applying a manufacturing technique for consuming the precursor at the first location to form the thin film on a substrate disposed in the thin film processing chamber; performing endpoint real-time monitoring and detection of at least one parameter selected from the group consisting of process parameters of the precursor synthesis chamber, process parameters of the thin film processing chamber, reaction by-product and wastewater parameters, and at least one property of the thin film; (i) providing feedback regarding the precursor consumption and the thin film formation to the precursor synthesis chamber to control the synthesis of the precursor such that the synthesis of the precursor occurs simultaneously or in conjunction with the thin film formation, (ii) the precursor synthesis rate matches the demands of the precursor consumption and thin film formation, and (iii) the precursor synthesis rate is synchronized with the precursor consumption rate for the formation of the thin film; 3. An integration method, comprising:

33. 33. The integrated method of claim 32, further comprising the step of comparing the amount or concentration of the precursor entering the thin film processing chamber with the amount or concentration of the precursor exiting the precursor synthesis chamber, calculating a difference, and utilizing the difference as part of an algorithm for controlling the precursor synthesis rate in the precursor synthesis chamber.

34. 33. The integrated method of claim 32, wherein the fabrication technique is one selected from the group consisting of chemical vapor deposition (CVD), atomic layer deposition (ALD), liquid plating, etching, atomic layer etching, ion implantation, and patterning.

35. 33. The integrated method of claim 32, wherein delivering the precursor from the precursor synthesis chamber to the thin film processing chamber is performed by use of at least one of vacuum, an inert gas, hydrogen, a reactive gas, or a combination of an inert gas and hydrogen reactive gas.

36. 33. The integrated method of claim 32, wherein the precursors are transported to the thin film processing chamber using an inert or reactive carrier gas.

37. 33. The integrated method of claim 32, wherein the precursor is volatilized or evaporated and transported to the thin film processing chamber using its own vapor pressure.

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