Methods and system for the integrated synthesis, delivery, and processing of source chemicals for thin film manufacturing

Abstract

An integrated system is provided for synthesizing a film-forming precursor, consuming the precursor, and forming a thin film on a substrate. The integrated system includes a raw material source, a precursor synthesis chamber communicating with the raw material source, a thin film processing chamber communicating with the precursor synthesis chamber, supplying the precursor from the precursor synthesis chamber to the thin film processing chamber in a controlled manner for consuming the precursor to form a thin film on the substrate, a monitoring system for monitoring thin film formation in the thin film processing chamber and / or precursor synthesis in the precursor synthesis chamber, and a controller for controlling the precursor synthesis rate, precursor consumption, and / or thin film formation. The precursor synthesis rate is synchronized with the precursor consumption rate for forming the thin film.

Description

Technical Field

[0001] Reference materials for comparison of related applications 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] This invention relates to methods and integrated systems for the synthesis, transport, delivery, and processing of source chemicals for thin film manufacturing, including, for example, deposition, etching, and patterning. Prior Technology

[0003] In various 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 phase deposition, etching (including atomic layer etching, partial and complete material removal processes), implantation (such as ion implantation), and patterning (i.e., forming a predefined structure in a deposited layer, such as forming a transistor pattern onto a silicon substrate), mainly include a five-step method as follows: (1) a precursor is manufactured or synthesized at a first location, such as a chemical manufacturing plant; (2) The precursors are then stored in leak-proof and spill-proof custom containers or dedicated storage facilities until they are ready to be shipped to the customer; (3) The precursors are then transported by land, air or sea to a second location, usually the customer’s factory, in leak-proof and spill-proof custom containers or dedicated storage facilities, where they are used to manufacture an apparatus or system; (4) The precursors remain stored in leak-proof and spill-proof custom containers or dedicated storage facilities at the second location until they are ready to be used; (5) Finally, the precursors are incorporated into the process carried out at the second location so that they can be used or consumed in the thin film growth, construction or formation as part of the apparatus or system manufacturing technology.

[0004] However, the conventional manufacturing methods discussed above suffer from various technical, safety, environmental, and economic inefficiencies and drawbacks. Conventional methods are hampered by their inability to transport chemicals with hazardous inhalation toxicity and / or instability due to impact sensitivity, the dangers of bulk storage, or the need for extensive cooling to maintain their integrity before use. Another major drawback is the unnecessarily extended time window and lengthy duration between precursor synthesis and actual use. This drawback results in a significant financial burden due to the capital expenditure associated with stockpiling and storing high-value precursors at chemical synthesis facilities before they are sold and transported to customer facilities for use. Current schemes also require the use of special containers to maintain the integrity of precursors until their use, adding another cost. Repetition in storage and transportation is inherent in precursor synthesis and consumption facilities. The dual handling, storage, processing, and disposal of byproducts from precursor synthesis at precursor synthesis facilities and precursor consumption at customer facilities incurs considerable additional costs. In addition, concerns about changes in product quality over time incur additional costs to ensure that products do not drift beyond target technical specifications from the time of manufacture to the time of consumption.

[0005] Equally important are the environmental, safety, and health hazards associated with transporting chemicals by air, sea, or land, as well as the destructive impacts on humans and the environment caused by chemical spills, such as those due to human error, failure of quality control, and / or other unforeseen incidents that may occur during transport and handling.

[0006] These drawbacks and limitations are illustrated in the semiconductor (i.e., computer chips) and heterogeneous device integrated circuit (IC) industries, where many of these conventional manufacturing methods are applied to equipment commonly referred to as batch, individual, and cluster manufacturing or processing equipment. Batch processing involves applying a manufacturing technique to multiple wafers simultaneously in a single manufacturing facility. In contrast, individual processing involves applying a manufacturing technique to a single wafer in a single facility before transporting it to a different batch, individual, or cluster manufacturing facility. Cluster processing, on the other hand, involves several single-wafer processing chambers and a wafer handling robot arm.

[0007] In recent years, clustered equipment processing has been increasingly used in various wafer fabrication processes, as described by A. Bowling in his paper "Single-Wafer Processing And Real-Time Process Control For Semiconductor Integrated Circuit Manufacturing," presented at the International Symposium on Semiconductor Manufacturing (A. Bowling, Int'l. Symposium on Semiconductor Mfg., (June 21-22, 1994, IEEE)). The single-wafer clustered equipment adopted by Applied Materials in the mid-1980s represented the last major successful introduction of a new manufacturing equipment method into the IC industry. Replacing most of the then-prevalent batch processing solutions with clustered equipment-based manufacturing enabled the IC industry to: reduce overall plant costs; embed computer-controlled sensors into manufacturing equipment for real-time diagnostics; achieve versatility in parallel implementation across different manufacturing methods; ensure rapid manufacturing cycle times; implement short cycle times to test material and process innovations; and achieve flexibility in simultaneously manufacturing various IC products. For example, these achievements are described on Applied Materials' website and in articles by M.M. Moslehi et al. and SM. George et al. (MM Moslehi et al., Single-Wafer Integrated Semiconductor Device Processing, IEEE Transactions on Electron Devices, V.39, pp.4-31 (1992); SM. George, Atomic Layer Deposition: An Overview, Chem. Rev., V. 110, pp.111-131 (2010).)

[0008] Cluster-type equipment manufacturing methods have been accepted under the premise of sequential processing requirements, such as CVD and ALD processes that require strict control of processing parameters, including exposure time, pressure, temperature, and other parameters. For example, cluster-type equipment is typically formed at multiple wafer processing stations placed around a central automated handling unit. The handling unit has a fixed precursor input, which is provided to each processing station, such as a deposition chamber. The input is typically a stable reservoir of gas or volatile substances. The wafer processed in the first deposition chamber then leaves the first deposition chamber within a specified time limit and is typically moved to another deposition chamber within the cluster-type tool under in-situ high vacuum conditions without breaking the vacuum.

[0009] Without in-situ high vacuum conditions, wafer-based equipment structures can suffer from quality issues due to residual precursor gases and byproducts, heat in the initial deposition chamber, cross-contamination from other deposition precursors or precursor byproducts, oxidation and external contaminants if the wafer is exposed to air during transport from one chamber to the next. In-situ transfer between processing stations under vacuum allows for strict management of the atmosphere or environment to ensure control and effectively eliminates contamination between process steps.

[0010] However, the generation and supply of precursors are independent of the clustering equipment. Therefore, the high level of automation and control used in clustering equipment does not extend to the generation of precursors themselves, but only to the controlled transport or supply of precursors to the deposition chamber. Furthermore, this approach inherently relies on maintaining the thermal stability and chemical integrity of the precursors under storage conditions until use.

[0011] Furthermore, the established push towards more complex and smaller semiconductor and heterogeneous device structures has led to increased limitations on established thin-film deposition methods. Specifically, due to the complexity and thermal brittleness of device structures, low thermal exposure during fabrication becomes absolutely necessary, where temperature variations can induce undesirable reactions within the substructure. This danger is described, for example, in a paper 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). Moreover, as film thickness approaches the atomic scale, thermally induced migration, in addition to electromigration, can alter the properties and performance of the film.

[0012] Another consideration is the desire to move toward more flexible substrates, such as plastic or polymer substrates, which typically cannot withstand the same processing temperatures as conventional substrates, such as silicon or gallium nitride, for example. See, for example, S. Majee et al., “Permeation barrier performance of Hot Wire-CVD grow silicon-nitride films treatment by argon plasma,” Thin Solid Films, V.575, pp.72-75 (2015).

[0013] Another consequence of pushing towards more complex and smaller fabrication structures is the impetus for integrating new materials and process technologies. While semiconductors in the 1990s used elements with a maximum of about 12 atoms, the International Technology Roadmap for Semiconductors projected that by 2015, nearly 50 atoms of elements would be used in semiconductor manufacturing. See, for example, B. Bottoms et al., ITRS Summer Conference, Roadmap Meeting, Stanford University, July 11-12, 2015; R. Allen et al., Summer Conference, Roadmap Meeting, Stanford University, July 11-12, 2015; S. Das, ITRS Architecture Workshop, February 26-27, 2015. When considering the compounds formed by the possible combinations of these different atomic elements, the diversity and complexity of materials (e.g., metals, semiconductors, insulators, dielectrics, etc.) are expanding at a near-exponential rate. However, this growth is severely limited by the inability to develop stable and transportable sources of volatile precursors that can be reacted reliably and in a controlled manner within the processing station of manufacturing equipment to form high-quality films.

[0014] Due to their complexity, the need to combine new materials and process technologies, as well as the extreme precision and tight control required in the formation of ultrathin films (e.g., as thin as an atomic layer), has further driven the trend toward more complex and smaller fabrication structures, resulting in increased costs associated with the manufacture of such structures.

[0015] Therefore, a method and system for the synthesis, delivery, and processing of precursors for thin film manufacturing that eliminates repetitive steps or reduces the number of steps in the process, thereby lowering the manufacturing costs of both conventional and novel raw materials and processes, would be desirable. Furthermore, methods that eliminate the thermal and chemical stability issues of precursors would expand the ability to deposit new desired thin film compositions, which is currently unattainable with conventional methods and systems. Moreover, such methods and systems are highly needed in multiple industrial sectors, including semiconductors (e.g., computer chips), aerospace, energy, sensors, medical, biological, chemical, and defense industries. Summary of the Invention

[0016] In one embodiment, the present invention relates to an integrated system for synthesizing a film-forming precursor, consuming the precursor, and forming a thin film on a substrate, wherein the rate of precursor synthesis is synchronized with the rate of consumption of the precursor for forming the thin film.

[0017] In another embodiment, the present invention relates to an integrated system for synthesizing a film-forming precursor, consuming the precursor, and forming a thin film on a substrate. The integrated system includes a raw material source containing at least one raw material; a precursor synthesis chamber including an inlet and an outlet, the inlet of the precursor synthesis chamber being connected to the raw material source to supply the raw material to the precursor synthesis chamber for reacting and synthesizing a precursor; a thin film processing chamber connected to the precursor synthesis chamber, the thin film processing chamber including an inlet directly connected to and communicating with the outlet of the precursor synthesis chamber to supply the precursor from the precursor synthesis chamber to the thin film processing chamber in a controlled manner for consuming the precursor and forming a thin film on a substrate in the thin film processing chamber; and a monitoring system for endpoint and real-time monitoring. The system includes a detection module for film formation in a thin film processing chamber and / or precursor synthesis in a precursor synthesis chamber; and a controller for: (i) receiving data from a monitoring system regarding precursor consumption and film formation, and transmitting the data to the precursor synthesis chamber to control the rate of precursor synthesis to ensure that the rate of precursor synthesis matches the requirements of precursor consumption and film formation; and / or (ii) receiving data from a monitoring system regarding precursor synthesis and transmitting the data to the thin film processing chamber to control the rate of precursor consumption and film formation to ensure that the rates of precursor consumption and film formation match the rate of precursor synthesis. The precursor synthesis rate is synchronized with the rate of precursor consumption used to form the thin film.

[0018] In another embodiment, the present invention relates to an integrated method for synthesizing a film-forming precursor, consuming the precursor, and forming a thin film on a substrate. The integrated method includes providing a raw material source containing at least one raw material at a first location; supplying at least one raw material from the raw material source to a precursor synthesis chamber at the first location; reacting at least one raw material in the precursor synthesis chamber to form a precursor at the first location; supplying the precursor from the precursor synthesis chamber in a controlled manner to a thin film processing chamber at the first location, the thin film processing chamber operating in parallel with and connected to the precursor synthesis chamber; using a manufacturing technique to consume the precursor to form a thin film on a substrate located in the thin film processing chamber at the first location; performing endpoint, real-time monitoring and detection of precursor consumption and thin film formation in the thin film processing chamber; and transmitting feedback on 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 and the formation of the thin film occur simultaneously or in parallel, (ii) the precursor synthesis rate is matched with the demand for precursor consumption and thin film formation, and (iii) the precursor synthesis rate is synchronized with the precursor consumption rate used to form the thin film.

[0019] In another embodiment, the present invention relates to an integrated method for generating a nickel tetracarbonyl precursor and forming a nickel thin film on a substrate. The method includes supplying bulk metallic nickel to a precursor generation chamber at a first location, sealing the precursor generation chamber, flushing the precursor generation chamber to remove adsorbed and residual gases, heating the bulk metallic nickel to a temperature of 80°C to 120°C, supplying carbon monoxide to the precursor generation chamber while simultaneously enabling flow communication between the precursor generation system and a downstream and interconnected thin film processing chamber to generate the tetracarbonyl nickel precursor, supplying the tetracarbonyl nickel precursor directly from the precursor generation chamber to the thin film processing chamber, heating the substrate in the thin film processing chamber to a temperature of 180°C to 250°C to decompose the tetracarbonyl nickel precursor on the substrate to form a nickel thin film, performing endpoint, real-time, in-situ monitoring and detection of nickel thin film formation in the thin film processing chamber, and transmitting feedback on nickel thin film formation to the precursor generation chamber to control the generation rate of the tetracarbonyl nickel precursor, such that the generation of the tetracarbonyl nickel precursor and the formation of the nickel thin film occur simultaneously or in parallel.

[0020] In another embodiment, the present invention relates to an integrated method for generating an azido acid precursor and forming a silicon nitride thin film on a silicon substrate. The method includes supplying a high-boiling-point hydroxyl liquid to a precursor generation chamber. The precursor generation chamber has a gas inlet at the bottom of the chamber adjacent to the liquid surface and a gas outlet above the liquid surface. The method further includes heating a hydroxyl liquid to a temperature of 40°C to 65°C to form a hydroxylated liquid; introducing a first stream of trimethyl azidosilane carried in a carrier gas into a precursor generation chamber via a gas inlet, wherein the trimethyl azidosilane reacts with the hydroxylated liquid to generate an azidoic acid precursor; supplying a second stream of azidoic acid carried in a carrier gas directly from the precursor generation chamber to a thin film processing chamber, the thin film processing chamber operating in parallel with and connected to the precursor generation chamber; heating a silicon substrate in the thin film processing chamber to a temperature of 325°C to 500°C, causing the azidoic acid to react with the silicon substrate to form a silicon nitride thin film; performing endpoint, real-time, in-situ monitoring and detection of silicon nitride thin film formation in the thin film processing chamber; and transmitting feedback on silicon nitride thin film formation to the precursor generation chamber to control the generation of the azidoic acid precursor, such that the generation of the azidoic acid precursor and the formation of the silicon nitride thin film occur simultaneously or in parallel.

[0021] In another embodiment, the present invention relates to an integrated method for generating a monosilaneamine precursor and forming a silicon nitride thin film on a silicon substrate. The method includes supplying a first stream of ammonia carried in a first carrier gas to a precursor generation chamber; supplying a second vapor of monochlorosilane in a second carrier gas to the precursor generation chamber to react with the first stream to generate a monosilaneamine precursor; supplying the monosilaneamine carried in the first and second carrier gases from the precursor generation chamber to a thin film processing chamber, the thin film processing chamber operating in parallel with and connected to the precursor generation chamber; consuming the monosilaneamine precursor using a manufacturing technique to form a silicon nitride thin film on a silicon substrate located in the thin film processing chamber; performing endpoint, real-time, in-situ monitoring and detection of the silicon nitride thin film formation in the thin film processing chamber; and transmitting feedback regarding the silicon nitride thin film formation to the precursor generation chamber to control the generation of the monosilaneamine precursor, such that the generation of the monosilaneamine precursor and the formation of the silicon nitride thin film occur simultaneously or in parallel.

[0022] Another embodiment of the present invention relates to an integration method for pulse-forming metal halide precursors that is timed to match the pulse requirements of atomic layer deposition (ALD).

[0023] According to the present invention, the novel integration of thin film formation requirements with the generation and consumption of precursors enables the practical deposition of thin film compositions under conditions previously considered impractical for end-to-end manufacturing. For example, in the case of highly toxic or potentially explosive precursors, the physical presence of the precursors can be controlled below toxicity or auto-accelerating decomposition hazard limits, allowing them to be consumed immediately during the process. Moreover, since the first and second chambers are connected and interconnected using tightly controlled valves and pumping systems, the integrity of the internal air in each chamber is maintained and isolated, while still allowing precise flow of gases, chemicals, and precursors between the chambers.

[0024] According to this invention, the novel integration of thin film formation requirements with the generation and consumption of precursors also allows for the use of chemicals and precursors that are highly unstable at room temperature, or that require extensive cooling to maintain their integrity before use. This invention also enables the formation or volatilization of novel and unconventional precursors and chemicals that are not yet commercially available and not currently used in manufacturing. This invention is also capable of forming or volatilizing known and desired precursors and chemicals that have been considered too toxic, too unstable, or dangerous for use in commercial thin film manufacturing and modification methods.

[0025] This invention also eliminates unnecessary steps in conventional processes that require the synthesis of precursors or chemicals at a first location, most commonly a chemical manufacturing plant, followed by the transport of the precursors to a second location, an equipment or system manufacturing plant, where they are consumed in a process. More specifically, this invention eliminates the step of transporting the synthesized precursors to the equipment or system manufacturing plant. Furthermore, this invention eliminates the need for expensive special containers that maintain the integrity of the chemicals before use; eliminates the inherent redundancy between chemical synthesis and storage and transport at customer facilities; and combines the dual handling, storage, processing, and disposal of byproducts from precursor synthesis at the chemical plant and the consumption of precursor chemicals at the manufacturing plant into a single byproduct disposal step at the manufacturing plant.

[0026] This invention also differs from the concept of point-of-use precursor generation. Generally, there are two types of point-of-use precursor generation. One type involves the in-situ formation of the precursor in the same chamber where thin film fabrication takes place, typically in a vapor space above the substrate. This type can be referred to as "in-situ point-of-use precursor generation." The second type involves the generation of the precursor in a container adjacent to the thin film processing or fabrication chamber, wherein the precursor is immediately transferred to the fabrication chamber or isolated / stored until later use. This type can be referred to as "non-in-situ" or "proximity" point-of-use precursor generation.

[0027] Both in-situ and ex-situ use point precursor generation have many inherent limitations and drawbacks. Examples of in-situ precursor generation are disclosed in U.S. Patent Nos. 6,730,367 and 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 film fabrication. Furthermore, due to the inherent characteristics of the chemical reactions involved in precursor synthesis, precise management of processing conditions is difficult to achieve in in-situ use precursor generation. These inherent characteristics may include the presence of starting materials, the generation of byproducts, and the heat or light from the reactions of multiple basic chemical components required for precursor synthesis. The side effects of such 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 reactor wall and / or substrate temperatures, and thermal or photosensitive damage to fragile substrates such as plastics and polymers. Because the basic chemical components are injected into a synthesis chamber isolated from where the actual chemical reaction occurs, and only the resulting precursors are introduced into the processing reactor, the present invention provides a more reliable and highly reproducible method.

[0028] Another limitation of in-situ precursor generation is the sequential nature of the synthesis and processing steps involved. In the first step, the processing chamber must be set with certain precursor synthesis parameters so that multiple basic components can react near or within the chamber to form the source precursor. Next, the processing chamber is flushed to remove all synthesis byproducts, and finally, the processing chamber is set with the actual substrate processing parameters (including substrate introduction) so that the precursor can decompose and the film can form. However, this sequential process of forming the precursor under the first set of parameters in the processing chamber, followed by waiting to change those parameters to make decomposition and film formation feasible, leads to undesirable delays in wafer yield (and thus, higher manufacturing costs).

[0029] The present invention addresses these problems by continuously synthesizing source precursors in a separate synthesis chamber and reliably and controllably feeding the source precursors into a processing chamber pre-set with desired processing parameters, wherein the source precursors are consumed simultaneously during the manufacturing or deposition process.

[0030] A further limitation of in-situ use of precursor generation is the challenge of preventing precursor synthesis byproducts from contaminating the processing chamber and substrate. Where necessary, the present invention addresses these problems by removing precursor synthesis byproducts from the precursor synthesis chamber before introducing the precursor into the processing chamber.

[0031] Another limitation of in-situ precursor generation is the concern that the basic chemical components used to synthesize the precursor and the byproducts of this synthesis may be harmful or damaging to the processing chamber, as they may cause undesirable etching, corrosion, or oxidation of the manufacturing chamber. This invention addresses these problems by synthesizing the source precursor in a separate synthesis chamber specifically designed and constructed to handle corrosive, oxidizing, or otherwise interfering basic chemicals and reaction byproducts, and to remove precursor synthesis byproducts before introducing the precursor into the processing chamber.

[0032] Another limitation of in-situ use point precursor generation is the lack of linkage between precursor synthesis and precursor consumption during the process. This limits the ability to precisely control the process to produce precise deposition results, such as films with precise thickness and composition. Precise linkage between precursor generation and deposition processes via an instrument feedback loop is an important aspect of this invention, as described in detail herein.

[0033] Examples of off-site or adjacent-site-of-use precursor generation are disclosed in JPven der Ziel, Applied Physics Letters, Vol. 71:6, pp.791-793 (1997); DNBuckley 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. A major limitation of off-site-of-use-site precursor generation is that precursor synthesis is not closely coupled with or synchronized with precursor consumption in the process, severely limiting the ability to precisely control the process to produce precise deposition results, such as films with precise thickness, desired morphology, physical and chemical properties, and composition. For the increasing importance of control in emerging processes, see, for example, A. Emami-Naeini et al., the 47th IEEE Workshop on Decision and Control, a symposium in honor of W. Wolovich, Cancun, Mexico (December 9-11, 2008). A key aspect of this invention is the precise connection of precursor generation and deposition processes via instrument feedback loops, as described in detail herein.

[0034] The instrument feedback loop can include in-situ and ex-situ monitoring and detection techniques, spectroscopy, and spectrometry to simultaneously monitor, control, and manage various parameters of the precursor synthesis process and membrane fabrication. These parameters may include, but are not limited to, temperature, pressure, feedstock and precursor flow rates, the chemical synthesis itself, and all operating conditions of the membrane fabrication process. In-situ and ex-situ detection techniques, spectroscopy, and spectrometry also enable endpoint, real-time, in-situ monitoring and detection. These facilities also enable the interaction, coupling, and closed-loop feedback between precursor synthesis parameters, membrane processing parameters, and reaction byproduct and effluent parameters.

[0035] Another limitation of off-site or near-point-of-use precursor generation is its failure to provide the critical feedback elements and information needed to ensure that precursor generation and delivery occur in a manner that ensures successful thin-film processing and achieves desired thin-film objectives. Conventional off-site or near-point-of-use precursor generation focuses solely on assessing the properties and characteristics of the precursor, such as quality (purity) and flow rate (amount delivered to the manufacturing chamber). In contrast, the present invention enables fairly desirable feedback, such as that determined by specific film properties measured in real time on the substrate. For example, in-situ sheet resistance and / or thickness measurements can be compiled during the process to provide real-time feedback on precursor generation and delivery. Simple Explanation of the Diagram

[0036] The following detailed description of preferred embodiments of the invention will be better understood when read in conjunction with the accompanying drawings. For the purpose of illustrating the invention, the presently preferred embodiments are depicted in the drawings. However, it should be understood that the invention is not limited to the precise arrangements and means shown. In the drawings:

[0037] Figure 1 is a schematic diagram of a precursor synthesis chamber connected to a thin film processing chamber according to one embodiment of the present invention;

[0038] Figure 2 is a schematic diagram of a system according to one embodiment of the present invention, the system comprising a precursor synthesis chamber, wherein a gaseous precursor is supplied to a thin film processing chamber via a manifold system.

[0039] Figure 3 is a schematic diagram of a system according to one embodiment of the present invention, the system comprising a precursor synthesis chamber and a liquid-phase precursor supplied to a thin film processing chamber via a manifold system.

[0040] Figure 4 is a schematic diagram of a system according to one embodiment of the present invention, the system comprising multiple precursor synthesis chambers connected to a single thin film manufacturing unit.

[0041] Figure 5 is a schematic diagram of a system according to one embodiment of the present invention, the system comprising multiple precursor synthesis chambers in fluid communication with multiple thin film processing chambers.

[0042] Figure 6 is a schematic diagram of a cluster-type device according to an embodiment of the present invention, the cluster-type device comprising multiple integrated precursor synthesis chambers and thin film processing chambers; and

[0043] Figure 7 is a schematic process diagram of a manufacturing technology according to one embodiment of the present invention, which includes a flexible substrate in the form of a continuous roll or roll material. Implementation

[0044] According to embodiments of the present invention, methods and systems are provided for achieving fully and tightly controlled processes and systems for fabricating thin film structures by utilizing real-time and in-situ analysis and control of the generation and consumption of reactive or difficult-to-process precursors, and for fully coupling and integrating precursor synthesis processes / systems with thin film formation processes / systems. The integrated synthesis, delivery, and processing of source chemicals is an advantageous implementation method for reproducible and reliable thin film fabrication.

[0045] The embodiments of the present invention can be applied to any process in any industrial environment, including but not limited to semiconductor (computer chips), aircraft, energy, sensors, medical, biological, chemical and defense industries.

[0046] Referring to Figure 1, the figure shows a schematic diagram of an integrated precursor synthesis (i.e., generation) and thin film deposition system 100, which includes a first chamber 101 connected to a second chamber 102, and more specifically, a precursor formation chamber 101 connected 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 precursor formation process implemented in parallel with one of the processes of thin film formation, etching, implantation, or patterning. In yet another embodiment, the invention relates to a cascaded configuration of a precursor formation chamber 101 (or precursor synthesis container or precursor synthesis chamber, these terms are used interchangeably herein) physically connected to a processing chamber 102, wherein the processing chamber 102 is a separate processing chamber or part of an overall processing chamber. The effluent or product from the precursor formation chamber 101 is transported directly to the tandem processing chamber 102 via a conduit or manifold system. Therefore, precursor formation is controlled, optimizing not only the synthesis but also the effective deposition of the precursor on the substrate within the processing chamber. This invention reliably fabricates novel thin film structures and expands the conditions under which conventional thin films can be manufactured.

[0047] The precursor formation chamber 101 may have one or more inputs required to carry out its operation, including raw material 104, facilities 109 such as electricity, and inputs from electronic monitoring and control instruments for managing and controlling the operation of the precursor formation chamber 101. More specifically, the integrated system 100 further includes a raw material source 104 and an associated feeding system that delivers the basic material or raw material of the precursor to the precursor formation chamber 101 in a controlled manner (using various control facilities 109, such as electricity, vacuum, heat, cooling, radiation, etc. via a first conduit 105 (i.e., raw material supply conduit) and a raw material inlet 106 for the synthesis of the precursor in the precursor formation chamber 101). The precursor formation chamber 101 is therefore not only a storage container for the precursor, but also a reactor in which the precursor raw material is generated by the raw material supplied to it.

[0048] The precursor formation chamber 101 further includes 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 via the outlet 107 and is then transported in a precisely controlled manner (using various control facilities 109, such as electricity) to the processing chamber 102 in solid, liquid, or vapor form via a second conduit 108 (i.e., a precursor transport conduit), where the synthesized precursor is processed to grow, etch, implant, or pattern a thin film. Thus, the precursor formation chamber 101 and the processing chamber 102 are connected to each other and directly communicate with each other.

[0049] In another embodiment (not shown), instead of separate chambers separated by a conduit, the precursor forming chamber and the processing chamber can constitute different chambers, zones, or areas within a single tank, and can be separated from each other within the tank by a common wall or partition. In such an embodiment, the wall or partition preferably includes through-holes equipped with valves and controllers for selectively isolating the chambers from each other, or allowing the precursor to flow from the precursor synthesis chamber to the processing chamber. Thus, although there is no precursor delivery conduit, the precursor synthesis chamber and the processing chamber will still be connected and directly communicated with each other.

[0050] In one embodiment, the precursor forming chamber 101 is preferably a precursor synthesis chamber. The precursor forming chamber 101 is also referred to below as the precursor synthesis chamber.

[0051] In one embodiment, the raw material supply conduit 105, the precursor transport conduit 108, the precursor synthesis chamber 101, and / or the processing chamber 102 are equipped with one or more valve assemblies 103 and electronic sensors (not shown). These are used for endpoint, real-time, in-situ monitoring and detection of raw material transport, precursor transport, thin film processing, and by-product processing. For example, such valves 103 and sensors enable the precursor to flow reliably, in a controlled, and consistent manner from the precursor synthesis chamber 101 to the thin film processing chamber 102. 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 that use devices such as O-rings or metal gaskets to effectively separate the environments of the two chambers 101, 102.

[0052] The precursor synthesis chamber 101 may also have a facility, system, or manifold 110 for discharging materials that are unnecessary or even harmful to the precursor synthesis. These materials may include fluids used to flush the chamber 101, synthesis reaction byproducts that may be generated during start-up of the chamber 101 or due to process disturbances, and / or precursors whose quality exceeds control limits or are required for film manufacturing or modification.

[0053] The precursor synthesis chamber 101 may also be equipped with in-situ and ex-situ monitoring and detection technologies, spectroscopy, and spectrometry to monitor and control various parameters of the precursor synthesis process. These parameters may include, but are not limited to, temperature, pressure, flow rates of feedstocks and precursors, and all operating conditions of the chemical synthesis itself. Electronic sensors and in-situ and ex-situ monitoring and detection technologies, spectroscopy, and spectrometry can also enable endpoint, real-time, in-situ monitoring and detection. These facilities can also enable the interaction, coupling, and one of the closed feedback loops between precursor synthesis parameters, thin film processing parameters, and reaction byproduct and effluent parameters. More specifically, the present invention allows for closed-loop precursor synthesis and thin film processing by using in-situ and / or ex-situ embedded sensors to control and manage the linkage between precursor generation / synthesis, precursor consumption, and thin film processing. 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.

[0054] Furthermore, this invention thus ensures precise and controlled management of precursor properties, such as the generation and feed rates into processing chamber 102; film formation properties, such as thickness and composition; and reaction byproducts and processing chamber effluent properties, such as chemical composition and flow rate. In some embodiments, monitoring and detection techniques include, but are not limited to, elliptic polarization techniques and mass spectrometry, as well as infrared, near-infrared, optical, and ultraviolet spectroscopy. In one embodiment, the amount or concentration of precursor leaving film processing or forming chamber 102 can be compared and evaluated relative to the amount or concentration of precursor leaving precursor synthesis chamber 101, and this difference is incorporated into an algorithm to control the precursor generation rate in precursor forming chamber 101 and / or the rate of transport and delivery to film manufacturing chamber 102. In a preferred embodiment, the amount of precursor generated in precursor forming / synthesis chamber 101 is controlled by an algorithm that takes into account film properties, such as elliptic polarization thickness or sheet resistance.

[0055] Precursor synthesis and thin film deposition processes can be performed in parallel or simultaneously, with feedback from one of chambers 101, 102 controlling the operation of the other chamber 101, 102. For example, thin film formation in the second chamber 102 (e.g., a processing chamber or deposition chamber, these terms are used interchangeably herein) is monitored, preferably continuously, and feedback is relayed to the precursor synthesis chamber 101 to control precursor formation / synthesis. In the simplest case, if there is no precursor requirement in the deposition chamber 102, precursor generation in the precursor synthesis chamber 101 is stopped. That is, precursor generation is combined with the requirement for thin film formation and matched with the introduction of co-reactants into the deposition chamber 102. Therefore, there is bidirectional communication between the precursor synthesis chamber 101 and the precursor deposition chamber 102, and the operation of the two chambers 101, 102 is controlled by a controller based on the monitoring parameters of each chamber 101, 102.

[0056] In some implementations, the manufacturing techniques are chemical vapor deposition (CVD), atomic layer deposition (ALD), liquid phase plating, etching (including atomic layer etching and partial and complete material removal processes), or patterning (i.e., forming a predefined structure into a pre-deposited layer, such as forming a transistor pattern into a silicon substrate).

[0057] In some embodiments, the controlled environment connected to the precursor synthesis chamber 101 and the processing chamber 102 is one of vacuum, inert gas, hydrogen, reactive gas, or a combination of these gases.

[0058] In some embodiments, processing chamber 102 is a batch processing unit, wherein manufacturing technology is applied simultaneously to multiple wafers in a single manufacturing facility. In other embodiments, processing chamber 102 is a single processing unit, wherein manufacturing technology is applied to a single wafer in a single-piece facility.

[0059] In some embodiments, the precursor molecules volatilize or evaporate and are transported into processing chamber 102 using their own vapor pressure, while in other embodiments, the precursor molecules are transported using an inert or reactive carrier gas. The precursor can be in liquid, solid, or gaseous form.

[0060] In some embodiments, the precursor synthesis chamber includes methods for separating byproduct chemicals, such as selective adsorption beds, like activated carbon, molecular sieves, or metal-organic frameworks, which remove byproducts from the gas-phase transport stream.

[0061] In a particularly preferred embodiment, the present invention relates to the integrated generation and consumption of toxic substances in a precursor synthesis reactor connected to a metal deposition chamber. For example, nickel tetracarbonyl is a precursor to nickel films and is a typical metallization process that can be carried out in a bundled precursor generation apparatus.

[0062] Nickel tetracarbonyl is highly toxic and carcinogenic at the ppm level. Its transport and storage are strictly limited or completely prohibited under local regulations. Furthermore, nickel tetracarbonyl exhibits only limited stability, slowly decomposing to form nickel and carbon monoxide even at room temperature. In one embodiment of the invention, bulk metallic nickel is loaded into a precursor synthesis chamber 101. The preferred form of nickel is a partially sintered nickel monolith retaining its porosity. Chamber 101 is sealed and then properly flushed and vented to eliminate adsorbed and residual gases. The nickel monolith is then heated to a temperature of 80°C to 120°C. During this stage, the opening of a valve in the precursor transport conduit 108 initiates a carbon monoxide flow, allowing it to flow from the precursor synthesis chamber 101 to the deposition chamber 102. The deposition chamber 102 is connected to a detector system, such as near-infrared, which can detect and determine the amount of precursor (i.e., nickel tetracarbonyl) present in the deposition chamber 102.

[0063] In deposition chamber 102, a substrate (not shown) is heated to a temperature of 180°C to 250°C. Nickel tetracarbonyl decomposes on the substrate to form a high-purity nickel film. Data from the nickel tetracarbonyl observation window and deposition chamber control are used to adjust the rate of nickel tetracarbonyl formation, thereby adjusting (preferably by a controller) the temperature of the sintered nickel monoliths and / or the rate of carbon monoxide flow. The proportion of excess carbon monoxide entering and / or leaving deposition chamber 102 can be measured and adjusted by program control to achieve optimal deposition rate and optimal film properties.

[0064] Under similar conditions, a cobalt film can be formed.

[0065] Another embodiment of the invention relates to the formation of silicon nitride using azidoacid at low temperatures. Azidoacid, also known as hydrogen azidoside, decomposes explosively when stored in bulk and has toxicity comparable to cyanide. Azidoacid decomposes at relatively low temperatures to form radical nitrogen products, including nitrogen-containing alkenes that can insert into Si-H bonds. Within deposition chamber 102, a silicon nitride film can be formed by nitriding amorphous hydrogen azidoside or by reacting azidoacid with a silane (or a higher grade polysilane) and a substrate in deposition chamber 102. In this invention, for example, azidoacid is formed as a low-concentration vapor in a series deposition chamber 102 along with a suitable inert carrier gas. A preferred method for generating azidoacid is to place a high-boiling-point hydroxyl liquid in a precursor synthesis chamber 101, with a bottom gas inlet below the liquid surface and a gas outlet above the liquid surface. Trimethyl azidosilane is carried in a gas stream that enters a hydroxyl liquid heated to 40-65°C. Trimethyl azidosilane reacts with the hydroxylated liquid to form, for example, harmless trimethylsilane stearyl alcohol, in the process of generating azidoic acid. The azidoic acid carried in the carrier gas then enters deposition chamber 102, where it reacts with an amorphous silicon hydride substrate at 325°-500°C to form silicon nitride. As in the aforementioned embodiments, the rate of azidoic acid formation in precursor synthesis chamber 101 is matched to its consumption rate in deposition chamber 102 by a suitable control mechanism. Another method for generating azidoic acid is to continuously produce it via a thermally driven reverse Diels-Adel reaction at elevated temperatures using a compound such as 4,7-methylene-3a,4,5,6,7,7a-hexahydrobenzotriazole.

[0066] Furthermore, those skilled in the art will understand that one or more of the above steps using examples of nickel tetracarbonyl or azidoacid can be used with any known precursor and the system / method of the present invention.

[0067] The present invention is also highly practical in that the stability of precursor reactants has a shorter timescale and their use is limited only by this factor, rather than toxicity. For example, graphene films are difficult to grow and modify. Such a method can form benzylene. At moderate concentrations and temperatures above 100°C, the stability of benzylene is on the order of seconds. Benzyne can be formed from intermediates such as 2-(trimethylsilyl)phenyltrifluoromethanesulfonate. In this embodiment, an inert gas-carried compound is passed through a heated block at an elevated temperature in a tandem precursor generation chamber 101 to form benzylene and the byproduct trimethylsilyltrifluoromethanesulfonate. The byproduct does not react with graphene, while benzylene reacts with graphene, thereby extending the polycyclic structure.

[0068] In another embodiment, the precursor can be synthesized via a combination of consumption and electrochemical synthesis. Examples of toxic precursors that can be generated include arsine, phosphine, germanane, and hydrogen selenide. Relatively unstable precursors, such as stanane, can also be generated similarly via consumption.

[0069] Another implementation related to thermal stability is the formation of silicon nitride. Tert-butylaminosilane has a half-life of several days at room temperature. However, it can be stable for several months at -40°C. In this case, the tandem precursor chamber 101 is formed by a refrigerated container capable of distributing the liquid into a carrier gas stream at an appropriate temperature for transport. With a substrate temperature of 300°C to 350°C and an ammonia co-reactant, a SiN film can be formed.

[0070] Another implementation of the advantage of simultaneous precursor generation and deposition is the cryogenic deposition of silicon nitride from monosilaneamine. At gas concentrations above approximately 2%, monosilaneamine self-reacts to form disilaneamine and ultimately trisilaneamine. Although monosilaneamine can form nitrogen-rich, amorphous hydrogenated silicon films at temperatures ranging from 200°C, there are currently no practical methods for storing and utilizing monosilaneamine. In this example, the tandem precursor chamber 101 is a plug flow reactor comprising a series of static flow mixers (not shown). Ammonia and monochlorosilane are introduced as separate gas streams in a suitable inert carrier gas. Adjusting the flow rate and concentration not only optimizes the generation of monosilaneamine but also minimizes unreacted monochlorosilane, disilaneamine, and trisilaneamine decomposition products. In this embodiment of the invention, the gas stream is first transferred from the deposition chamber 102 and analyzed by mass spectrometry (RGA), and is only allowed to enter the deposition chamber 102 if the gas stream is within the control parameters.

[0071] In another embodiment, a precursor synthesis chamber is used for the controlled synthesis of metal heavy halides. A quartz tube filled with granular or reactive metals, such as silicon, titanium, or tantalum, is placed inside an induction furnace. The tube's shape allows vapors of heavy halides, bromine, or iodine to pass through the granular material. A pulsed heating system, induction heating the metal to a temperature allowing reaction with the halogen, is coordinated with the consumption pulses of ALD in the deposition chamber. In one specific embodiment, polycrystalline silicon particles are filled in a quartz tube, and iodine vapor heated to above 200°C is introduced into the silicon-filled bed. Coordinated with a 1-minute ALD pulse duration, the temperature of the metallic silicon is induction heated to 650°C to 1000°C for 1 minute, and the formation rate of silicon tetraiodide is controlled using the amount of iodine in vapor form, which is then controlled to match the requirements of the ALD pulses in the film formation chamber. The induction heating pulses control 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 zone, which controls the temperature of the silicon tetraiodide vapor, preferably between 125°C and 350°C, to prevent the formation of solid silicon tetraiodide. In the film-forming chamber, the silicon tetraiodide chamber is alternately purged with pulsed and inert gas, followed by ammonia purging, and then another inert gas purging. In this way, a silicon nitride film is formed. Similarly, other metal halides can be formed by substituting metals. Depending on the conditions in the film-forming chamber and the alternating reactants, nitride, oxide, and metal (zero-valent) films can be formed.

[0072] In another embodiment, two reactant gases and, optionally, a carrier gas are introduced into a precursor synthesis chamber 101, with the effluent entering a thin-film processing chamber 102. The precursor synthesis chamber contains a series of mixing chambers, possibly including a static mixer, and may be equipped with heating or cooling mechanisms. Under appropriate pressure, the carrier gas and one reactant gas are introduced into the first stage of the static mixing chamber, controlled by a mass flow meter. Before the next static mixing element, a second reactant gas is again introduced into the synthesis stream under the control of a mass flow meter. If the reaction is highly exothermic, cooling may be required for the second stage. However, at least two stages are thermally controlled using a jacket with circulating liquid or another known thermal control method. Upon exiting the static mixing element, the product stream is analyzed by residual gas analysis (RGA), mass spectrometry, NIR (near-infrared), or UV analysis.

[0073] The flow is initially diverted to a reduction process via a suitable valve. However, once the appropriate precursor ratio is reached, the flow path leads directly into processing chamber 102, where the utilization of the active ingredient is monitored. When the thin-film process is complete, as measured by elliptic polarization, sheet resistance, or other suitable parameters, the introduction of the reactive gas into precursor synthesis chamber 101 is stopped by a control loop that closes the valve located before the mass flow meter. Preferably, a byproduct removal stage is included in the process flow as part of precursor synthesis chamber 101. Byproduct removal elements may include, for example, a cryogenic trap, an adsorption step, or a unique chemical reaction process specific to the byproduct.

[0074] In another embodiment, particularly when monosilaneamine is used for silicon nitride deposition, monosilaneamine and ammonia reactants (which can also act as a carrier gas) or nitrogen (which can act as a different carrier gas) are introduced into the first stage of a static mixer. Monochlorosilane is introduced into the stream before the second static mixing element as a homogeneous mixture leaving the first stage. A mass flow meter controls the amount and concentration of monosilaneamine formed in the second static mixing element using analytical information obtained from an RGA. Before or after analysis, the byproduct ammonium chloride can be removed by passing the process flow through a packed bed of granulated carbon, preferably cooled to below -10°C. However, in some cases, this step is not necessary because ammonium chloride can pass directly through the thin film processing chamber 102 without affecting the deposition process.

[0075] In another embodiment, two interconnected sub-chambers correspond to a precursor synthesis chamber 101. The purpose of the first sub-chamber is to carry liquid reactants into a gas stream, which in turn transfers the controlled reactants to the second sub-chamber, where the reaction occurs by reacting with relatively non-volatile raw materials to form a volatile precursor that enters the thin-film processing chamber 102 under controlled conditions. Byproducts are retained in the second sub-chamber. It should be noted that the reactant volume in the first sub-chamber is depleted, but the second sub-chamber, containing byproducts, is not necessarily depleted. The first sub-chamber can be considered similar to what is known in the art as a bubbler, in which a container holds a volatile liquid and a slanted tube that allows a gas to be introduced below the surface of the liquid reactants, and as the gas passes through the liquid phase, it carries the liquid in a vapor stream that exits the chamber above the liquid level. The amount of reactants carried is controlled by the rate of the carrier gas passing through the bubbler and the temperature of the liquid in the sub-chamber. The carried reactants then proceed through the slanted tube to the second sub-chamber, which functions as a reactor. The reaction chamber is equipped with an inclined tube and is typically heated under stirring and includes a vapor phase outlet connected to the thin film processing chamber 102. The reaction chamber contains a second non-volatile reactant. In a preferred embodiment, the contact time with the carried reactant is sufficient to ensure complete consumption of the volatile reactant, and the gas stream exiting the reaction chamber contains the carrier gas and volatile precursors for thin film synthesis.

[0076] As stated herein, apart from the substances carried by the carrier gas, the loaded reactants and byproducts are the only raw materials leaving the precursor synthesis chamber 101. However, a significant extension of this concept is the replenishment and replacement of reactive raw materials and byproducts within the precursor synthesis chamber 101 in a controlled process.

[0077] One embodiment involves azidoic acid (hydrogen azidoside), wherein trimethyl azidosilane is loaded into a bubbler. A second sub-chamber is loaded with stearyl alcohol (octadecyl alcohol) and heated to a temperature >60°C (above the melting point of stearyl alcohol) and stirred. A nitrogen stream carries the trimethyl azidosilane, which reacts with stearyl alcohol to form the volatile precursor azidoic acid, which is carried into the thin film processing chamber 102 as a nitrogen carrier gas. The byproduct stearoxytrimethyl silane is non-volatile and remains in the reaction chamber.

[0078] It should be understood that the above discussion regarding Figure 1 and the related preferred embodiments also applies to Figures 2-7, as discussed in detail below.

[0079] Referring to Figure 2, a schematic diagram of a system including a precursor synthesis chamber 201 is shown. The precursor synthesis chamber 201 is supplied with gaseous precursors and connected to a thin film processing chamber 202 via a manifold system 206 appropriately equipped to transport gaseous, liquid, or solid precursors in gaseous or vapor form. The precursor raw materials or basic raw materials are supplied from a raw material source (not shown). The manifold system 206 may include an electronic mass flow meter or a solid or liquid transport system. The manifold system 206 may also include additional equipment and controllers, such as a flushing gas system 203 and a corresponding venting system 205, to flush and / or vent the conduits or pipes 207 connecting the precursor synthesis chamber 201 and the thin film processing chamber 202.

[0080] In one embodiment, the manifold system 206 may also include various mechanisms and controls, generally designated 204, to regulate the gas, for example by means of electronic stabilizers to smooth changes in the adsorption of impurities that may be generated during the transfer from the precursor synthesis chamber 201 to the processing chamber 202. The transfer process may also include additional mechanisms for monitoring and controlling the transfer, such as temperature, pressure, and flow rate.

[0081] Referring to Figure 3, which illustrates a schematic diagram of a precursor synthesis chamber 301, the liquid precursor is supplied or transported to a thin film processing chamber 302 via a manifold system 306, which is suitably configured to transport the liquid precursor. The precursor can be in solid or liquid form, supplied from a feed source (not shown), with solid precursors undergoing liquefaction or melting processes, or dissolved in a suitable liquid or solvent before being transported to the thin film processing chamber 302. Additional equipment and controls for the manifold system 306 include a solvent system 303 for cleaning or removing residual precursor from the pipeline (i.e., delivery conduit) 307, a flushing system 304 for removing residual solvent from the delivery conduit 307, a corresponding discharge system 308 for cleaning and / or emptying the delivery conduit 307, and a solvent waste assembly 309. Various instruments and controls 305 may also be included to manage and control the delivery of an appropriate amount of precursor of suitable purity to the processing chamber 302. Such equipment may include instruments for monitoring temperature, pressure, and flow; instruments for treating precursors to remove particulates or other impurities; or instruments for evaporating liquid precursors before they are introduced into the thin film processing chamber 302.

[0082] Referring to Figure 4, a schematic diagram of an embodiment of a system is shown, comprising multiple precursor synthesis chambers 404a, 404b, and 404c connected in a controlled environment to a single thin film fabrication station or processing chamber 403. Multiple precursors are synthesized in precursor synthesis chambers 404a-404c and then simultaneously or sequentially conveyed to processing chamber 403, where they are consumed in a fabrication (e.g., deposition) process. Precursor synthesis chambers 404 may be configured with their own gas or liquid delivery systems, or other subsystems, as described above with reference to Figures 1-3, which may be necessary for the overall operation of the system.

[0083] Precursor synthesis chambers 404a-404c can be configured in various ways. For example, some or all of the precursor synthesis chambers 404a-404c can be arranged in parallel (i.e., see chambers 404a and 404b in FIG. 4), such that one or more precursors are simultaneously fed from each chamber 404a-404c to the deposition chamber 043. Alternatively, some or all of the precursor synthesis chambers 404a-404c can be configured in series or tandem arrangement (i.e., see chambers 404b and 404c in FIG. 4), wherein one or more precursor systems are sequentially fed 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 precursor mixture is fed to the processing chamber 403. Any other arrangement that can be formed by a combination of parallel and tandem arrangements may also be included. Moreover, the parallel arrangement of the chambers can be operated sequentially, simultaneously, or in any other combination as needed to create the desired effect in the thin film processing chamber 403. A wafer handling system 401 is also provided to move the substrate wafer between the storage box 402 and the thin film processing chamber 403.

[0084] Referring to Figure 5, which illustrates a schematic diagram of an embodiment of a system comprising multiple precursor synthesis chambers (PSCs) 504a, 504b in fluid communication with multiple thin film processing chambers (TPCs) 505a, 505b. Each precursor synthesis chamber 504a, 504b is equipped with a gas or liquid delivery system, as described above with reference to Figures 1-3. The wafer handling system 501 of Figure 5 includes a mechanism 502, in this example a robotic arm, for transferring substrate wafers between a storage cassette 503, the various thin film processing chambers 505a, 505b, and one or more metering (M) chambers 506 for monitoring the characteristics of each substrate wafer as it travels 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 system's operating mode is configured such that the substrate wafer can only enter one of the thin film processing chambers 505a and 505b, or any combination of the thin film processing chambers 505a and 505b, which may be required for overall process optimization or fabrication of single-layer or multi-layer thin films or structures. The process may include individual processing steps, such as film deposition, etching, ion implantation, or patterning, or a combination of processing steps, such as a complete set or subset of deposition, etching, ion implantation, and patterning procedures.

[0085] Referring to Figure 6, an embodiment of a cluster-type device is illustrated. This cluster-type device includes multiple integrated precursor synthesis chambers or generators 603a, 603b, 603c, 603d, 603e and thin film processing chambers 602a, 602b, 602c, 602d, 602e located around a central automated conveying unit, with a fixed precursor input supply to each processing chamber 602a, 602b, 602c, 602d, 602e. The effluent from the precursor synthesis chambers 603a, 603b, 603c, 603d, and 603e can be directed from the thin film processing chambers 602a, 602b, 602c, 602d, and 602e to a safe location (e.g., a washer) 609 until the thin film processing chambers 602a, 602b, 602c, 602d, and 602e have been fully adjusted and ready to introduce the precursors, and the precursors have been determined to exhibit the specifications and characteristics required for the thin film processing.

[0086] The substrate wafer is transferred from storage cassette 601 to thin film processing chambers 602a, 602b, 602c, 602d, and 602e (or other chambers may be included for the overall utility of the clustered equipment) via robotic arm 608 or other automated systems. Precursor synthesis chambers 603a, 603b, 603c, 603d, and 603e are each connected to a raw material source via conduits (not shown), as described above with reference to FIG1, and may be equipped with advanced technologies for controlling precursor synthesis, for example, maintaining specific precursor purity and flow rate in thin film processing chambers 602a, 602b, 602c, 602d, and 602e.

[0087] Referring to Figure 6, this control loop concept is provided for a precursor synthesis chamber 603c. However, it should be understood that this control loop can be applied to any one or more of the other precursor synthesis chambers 603a, 603b, 603d, and 603e, and its application can be in the same manner or with modifications to meet different control objectives for different precursors or thin film 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 processing chamber 602c, the precursor synthesis chamber 603c, or both. For example, the thin film processing chamber 602c may be equipped with a processing chamber sensor 604, and the precursor synthesis chamber 603c may be equipped with a chemical generator sensor 605. Signals from these sensors 604, 605 are processed via function block 606 to provide input to a controller 607 (more specifically, a chemical generator controller), which adjusts the operation of the precursor synthesis chamber 603c to meet production objectives. These instruments may include electronic sensors for endpoint, real-time, in-situ monitoring and detection, and / or in-situ and non-in-situ monitoring and detection techniques, as well as electronic sensors for spectroscopic and spectrometric methods, to monitor and control various parameters of the precursor synthesis process.

[0088] In some embodiments, the system includes one or more interconnected manufacturing or processing chambers or multiple chambers arranged sequentially or in series, wherein the manufacturing technology is applied to a continuous substrate, wherein the substrate is moved sequentially through one chamber and from one chamber to the next, undergoing one or more manufacturing technologies. An example of this embodiment is the roll-to-roll coating of a continuous film on a flexible substrate. In one such embodiment, one or more precursor synthesis modules or chambers are connected to the manufacturing or processing chambers, and the one or more precursors are conveyed to or sprayed onto the flexible substrate in vapor or liquid form, where they are decomposed or processed to form a thin film on the flexible substrate.

[0089] More specifically, referring to Figure 7, the figure illustrates the application of manufacturing techniques to flexible substrates in the form of continuous rolls or reels (e.g., strips, rolls, or spools), rather than in the form of discrete or individual units (e.g., wafers). The raw material roll 701 of the flexible substrate is unrolled or spread out and fed in a controlled manner into one or more interconnected manufacturing or processing chambers 703a, 703b, configured sequentially or in series, and exposed to a series of one or more manufacturing techniques designed to produce a target thin film structure on the flexible substrate. The manufacturing techniques may include identical processing steps, such as film deposition, etching, ion implantation, or patterning. Alternatively, the manufacturing techniques may include a combination of processing steps, such as a complete set of a subset of deposition, etching, ion implantation, and patterning procedures, each processing step within its specific processing or manufacturing chamber.

[0090] The manufacturing processes are preferably isolated from each other and each is enclosed within its own dedicated processing chambers 703a, 703b. One or more intermediate chambers 704 (e.g., measurement chambers) are preferably provided to increase isolation and / or process control. Each processing chamber 703a, 703b is associated with one or more precursor synthesis chambers 705a, 705b. The precursor synthesis chambers 705a, 705b can each deliver the same precursor in vapor or liquid form to each individual manufacturing or processing chamber 703a, 703b, wherein the precursor is completely or partially decomposed, processed, or consumed to form a film on the flexible substrate. Alternatively, each precursor synthesis chamber 705a, 705b can deliver different precursors in vapor or liquid form to the corresponding manufacturing or processing chamber 703a, 703b, wherein each precursor system is completely or partially decomposed, processed, or consumed to form a multilayer film of one layer on the flexible substrate.

[0091] A control manifold is incorporated to provide feedback and feedforward control to individual precursor synthesis chambers 705a, 705 to meet specified preset processing setpoints 710a, 710b. This control manifold includes measuring instruments 707a, 707b, and 708, and converter processing modes 709a, 709b connected to process controllers 706a, 706b via lines or conduits 711a, 711b. The resulting processed flexible substrate is wound onto end rollers 702. In one embodiment, instruments 707a, 707b are in-situ sensors, while instrument 708 is a non-in-situ sensor. In one embodiment, program controllers 706a, 706b are chemical source (i.e., precursor) controllers, and converter processing modes 709a, 709b are signal converters.

[0092] In some embodiments, one or more precursors are decomposed or processed on a flexible substrate using sol-gel or deposition 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, depending on the number of different precursors used, the resulting film comprises a single uniform layer or multiple layers.

[0093] As will be understood from the above discussion, the present invention can be embodied in various specific forms, including but not limited to the following: [Specific Example 1.] An integrated system for synthesizing a film-forming precursor, consuming the precursor, and forming a thin film on a substrate, wherein the precursor synthesis rate is synchronized with the precursor consumption rate for forming the thin film. [Specific Example 2.] An integrated system for synthesizing a film-forming precursor, consuming the precursor, and forming a thin film on a substrate, the system comprising: A source of raw materials containing at least one ingredient; A precursor synthesis chamber including an inlet and an outlet, wherein the inlet of the precursor synthesis chamber is connected to the raw material source to supply the raw material to the precursor synthesis chamber for reaction and synthesis of a precursor; A thin film processing chamber connected to the precursor synthesis chamber, the thin film processing chamber including an inlet directly communicating and connected 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, so as to consume the precursor to form a thin film on a substrate in the thin film processing chamber; A monitoring system for endpoint, real-time monitoring and detection of film formation in the thin film processing chamber and / or precursor synthesis in the precursor synthesis chamber; and A controller is configured to: (i) receive data from the monitoring system regarding precursor consumption and thin film formation, and transmit the data to the precursor synthesis chamber for controlling the rate of precursor synthesis to ensure that the rate of precursor synthesis matches the requirements of precursor consumption and thin film formation; and / or (ii) receive data from the monitoring system regarding precursor synthesis and transmit the data to the thin film processing chamber for controlling the rate of precursor consumption and thin film formation to ensure that the rate of precursor consumption and thin film formation matches the rate of precursor synthesis. The precursor synthesis rate is synchronized with the precursor consumption rate used to form the thin film. [Specific Example 3.] As in the integrated system of Specific Example 2, the controller is configured to compare the amount or concentration of precursor entering the thin film processing chamber with the amount or concentration of precursor leaving the precursor synthesis chamber to calculate the difference, and use the difference as part of an algorithm to control the rate of precursor synthesis in the precursor synthesis chamber. [Specific Example 4.] The integrated system of Specific Example 2, wherein the system is a closed-loop system, includes the precursor synthesis chamber and the thin film processing chamber connected thereto, and wherein the monitoring system and the controller control and manage the communication between the precursor synthesis in the precursor synthesis chamber and the consumption of precursors for forming the thin film in the thin film processing chamber. [Specific Example 5.] As in the integrated system of Specific Example 2, the controller adjusts the rate of precursor synthesis based on the rate of precursor consumption. [Specific Example 6.] The integrated system of Specific Example 2, wherein the monitoring system includes at least one of in-situ monitoring and detection technology, non-in-situ monitoring and detection technology, spectroscopy and spectrometry, to monitor at least one parameter of the precursor synthesis chamber and the thin film processing chamber. [Specific Example 7.] As in the integrated system of Specific Example 6, the at least one parameter is selected from the group consisting of temperature, pressure, flow rate of the one or more raw materials, flow rate of the precursor and reaction conditions for precursor synthesis. [Specific Example 8.] As in the integrated system of Specific Example 6, the in-situ and in-situ monitoring and detection techniques include a group of techniques selected from the group consisting of elliptic polarization technique, mass spectrometry, infrared spectroscopy, near-infrared spectroscopy, spectrophotometry and ultraviolet spectroscopy. [Specific Example 9.] The integrated system of Specific Example 2, wherein the monitoring system includes at least one of at least one in-situ embedded sensor and at least one off-situ embedded sensor for real-time monitoring and detection of at least one parameter. [Specific Example 10.] As in the integrated system of Specific Example 9, the at least one in-situ embedded sensor and / or the at least one non-in-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. [Specific Example 11.] As in the integrated system of Specific Example 9, the at least one parameter is selected from the group consisting of temperature, pressure, flow rate of the one or more raw materials, flow rate of the precursor and reaction conditions for precursor synthesis. [Specific Example 12.] As in the integrated system of Specific Example 2, the precursor synthesis chamber and the thin film processing chamber are separate and different chambers, and the internal environments of the precursor synthesis chamber and the thin film processing chamber are isolated from each other by valve assemblies. [Specific Example 13.] As in Specific Example 2, the integrated system wherein the precursor synthesis chamber includes an outlet to drain flushing fluid or reaction byproducts. [Specific Example 14.] The integrated system of Specific Example 2 further includes a manifold system that connects the outlet of the precursor synthesis chamber to the inlet of the thin film processing chamber for the flow of gaseous precursors. [Specific Example 15.] The integrated system, as in Specific Example 14, further includes a flushing gas system and a discharge system, which are conduits for flushing and venting the manifold system. [Specific Example 16.] The integrated system of Specific Example 2 further includes a manifold system that connects the outlet of the precursor synthesis chamber to the inlet of the thin film processing chamber for the flow of liquid phase precursors. [Specific Example 17.] The integrated system of Specific Example 16 further includes a cleaning system configured to supply a solvent solution to the conduit of the manifold system for cleaning the conduit, and a flushing system for removing residual solvent solution from the conduit of the manifold system. [Specific Example 18.] The integrated system, as in Specific Example 2, includes multiple precursor synthesis chambers connected to a single thin film processing chamber. [Specific Example 19.] As in Specific Example 18, in an integrated system, at least two of the plurality of precursor synthesis chambers are configured to be arranged in parallel such that precursors are simultaneously transported from each of the parallel-arranged precursor synthesis chambers to the single thin film processing chamber. [Specific Example 20.] As in the integrated system of Specific Example 18, at least two of the plurality of precursor synthesis chambers are configured to be arranged in series or cascaded, such that a precursor from an upstream precursor synthesis chamber is conveyed to a downstream precursor synthesis chamber to form a mixture of precursors, and the mixture of precursors is then conveyed from the downstream precursor synthesis chamber to the single thin film processing chamber. [Specific Example 21.] The integrated system, as in Specific Example 2, includes multiple precursor synthesis chambers connected to multiple thin film processing chambers. [Specific Example 22.] The integrated system of Specific Example 21 further includes: a storage box for storing at least one substrate; a plurality of measurement chambers for monitoring at least one characteristic of the substrate; and a transfer mechanism for transferring the substrate between the storage box, the plurality of thin film processing chambers and the plurality of measurement chambers. [Specific Example 23.] The integrated system of Specific Example 21 further includes a cluster-type device integrated with the plurality of precursor synthesis chambers and the plurality of thin film processing chambers. [Specific Example 24.] The integrated system as in Specific Example 21, wherein each precursor synthesis chamber is connected to a corresponding thin film processing chamber to deliver the same precursor in vapor or liquid form to the corresponding thin film processing chamber. [Specific Example 25.] As in the integrated system of Specific Example 21, each precursor synthesis chamber is connected to a corresponding thin film processing chamber to deliver a different precursor in vapor or liquid form to the corresponding thin film processing chamber. [Specific Example 26.] As in the integrated system of Specific Example 21, the substrate is a flexible substrate in the form of a continuous roll or reel, such as a strip, roll, tape or spool. [Specific Example 27.] As in the integrated system of Specific Example 26, the flexible substrate includes an unfolded or unrolled roll of raw material, which is supplied in a controlled manner to one or more of the plurality of interconnected thin film processing chambers. [Specific Example 28.] The integrated system of Specific Example 27, wherein the interconnected thin film processing chambers use the same manufacturing technology on the substrate. [Specific Example 29.] As in the integrated system of Specific Example 27, each of the interconnected thin film processing chambers uses a different manufacturing technology on the substrate. [Specific Example 30.] As in the integrated system of Specific Example 2, the precursor is selected from the group of chemicals that are unstable at room temperature. [Specific Example 31.] The integrated system as in Specific Example 2, wherein the precursor is one of nickel tetracarbonyl and azido acid. [Specific Example 32.] As in Specific Example 2, the integrated system wherein the thin film processing chamber is one of a batch machine, a single machine, and a clustered device. [Specific Example 33.] An integration method for synthesizing a film formation precursor, consuming the precursor, and forming a thin film on a substrate, the method comprising: A source of raw materials containing at least one ingredient is provided at the first location; At least one raw material from the raw material source is supplied to a precursor synthesis chamber at the first location; At least one raw material in the precursor synthesis chamber is reacted to form a precursor at the first location; The precursor is supplied in a controlled manner from the precursor synthesis chamber to the thin film processing chamber at the first location, the thin film processing chamber operating in parallel with and connected to the precursor synthesis chamber; A manufacturing technique is used to consume precursors to form a thin film on a substrate located in the thin film processing chamber at the first location; Perform endpoint monitoring and detection of precursor consumption and film formation in the thin film processing chamber; and Feedback on precursor consumption and film formation is transmitted to the precursor synthesis chamber to control the synthesis of precursors such that (i) the synthesis of precursors occurs simultaneously or in parallel with film formation, (ii) the rate of precursor synthesis is matched with the requirements of precursor consumption and film formation, and (iii) the rate of precursor synthesis is synchronized with the rate of precursor consumption used to form the film. [Specific Example 34.] The integration method of Specific Example 33 further includes comparing the amount or concentration of precursor entering the thin film processing chamber with the amount or concentration of precursor leaving the precursor synthesis chamber to calculate the difference, and using the difference as part of an algorithm to control the precursor synthesis rate in the precursor synthesis chamber. [Specific Example 35.] The integration method as in Specific Example 33, wherein the manufacturing technology is selected from the group consisting of chemical vapor deposition (CVD), atomic layer deposition (ALD), liquid phase plating, etching, atomic layer etching, ion implantation and patterning. [Specific Example 36.] The integration method of Specific Example 33, wherein the supply of the precursor from the precursor synthesis chamber to the thin film processing chamber is carried out by using at least one of vacuum, inert gas, hydrogen, reactive gas or a combination of inert gas and hydrogen reactive gas. [Specific Example 37.] The integration method of Specific Example 33, wherein the precursor system is delivered to the thin film processing chamber using an inert or reactive carrier gas. [Specific Example 38.] The integration method as in Specific Example 33, wherein the precursor is volatilized or evaporated and transported to the thin film processing chamber using its own vapor pressure. [Specific Example 39.] An integration method for generating a nickel tetracarbonyl precursor and forming a nickel thin film on a substrate, the method comprising: Bulk nickel is supplied to the precursor generation chamber located in the first position; Seal the precursor generation chamber; The precursor generation chamber is flushed to remove adsorbed and residual gases; Heat the bulk nickel metal to a temperature of 80°C to 120°C; Carbon monoxide is supplied to the precursor generation chamber while simultaneously enabling flow communication between the precursor generation system and downstream and interconnected thin film processing chambers to generate a nickel tetracarbonyl precursor, which is then supplied directly from the precursor generation chamber to the thin film processing chamber. The substrate in the thin film processing chamber is heated to a temperature of 180°C to 250°C, causing the nickel tetracarbonyl precursor to decompose on the substrate to form a nickel thin film. Perform end-point, real-time, in-situ monitoring and detection of nickel thin film formation in the thin film processing chamber; and Feedback regarding nickel film formation is transmitted to the precursor generation chamber to control the generation rate of the nickel tetracarbonyl precursor, so that the generation of the nickel tetracarbonyl precursor and the formation of the nickel film occur simultaneously or in parallel. [Specific Example 40.] An integration method for generating an azido acid precursor and forming a silicon nitride thin film on a silicon substrate, the method comprising: A high-boiling-point hydroxyl liquid is supplied to a precursor generation chamber, which has a gas inlet at the bottom of the chamber near the liquid surface and a gas outlet above the liquid surface; The hydroxyl liquid is heated to a temperature of 40°C to 65°C to form a monohydroxylated liquid; A first stream of trimethyl azidosilane carried in a carrier gas is introduced into the precursor generation chamber through a gas inlet, where trimethyl azidosilane reacts with a hydroxylation liquid to generate an azidoic acid precursor. A second stream of azidoic acid carried in a carrier gas is supplied directly from the precursor generation chamber to a thin film processing chamber, which operates in parallel with and is connected to the precursor generation chamber. The silicon substrate in the thin film processing chamber is heated to a temperature of 325°C to 500°C, so that azidoic acid reacts with the silicon substrate to form a silicon nitride thin film; Implement endpoint, real-time, in-situ monitoring and detection of silicon nitride film formation in the thin film processing chamber; and Feedback regarding the formation of silicon nitride films is transmitted to the precursor generation chamber to control the generation of azido acid precursors, so that the generation of azido acid precursors occurs simultaneously or in parallel with the formation of silicon nitride films. [Specific Example 41.] An integration method for generating a monosilaneamine precursor and forming a silicon nitride thin film on a silicon substrate, the method comprising: Ammonia carried in the first carrier gas is supplied in a first stream to the precursor generation chamber; The second vapor of monochlorosilane in the second carrier gas is supplied to the precursor generation chamber to react with the first stream and generate a monosilane amine precursor; A monosilaneamine precursor carried in first and second carrier gases is supplied from the precursor generation chamber to a thin film processing chamber, which operates in parallel with and is connected to the precursor generation chamber. A manufacturing technique is used to consume a monosilaneamine precursor to form a silicon nitride film on a silicon substrate located in the thin film processing chamber; Perform end-point, real-time, in-situ monitoring and detection of silicon nitride thin film formation in the thin film processing chamber; and Feedback regarding the formation of silicon nitride films is transmitted to the precursor generation chamber to control the generation of monosilaneamine precursors, such that the generation of monosilaneamine precursors occurs simultaneously or in parallel with the formation of silicon nitride films. [Specific Example 42.] The integration method as in Specific Example 41, wherein the precursor generation chamber is a plug flow reactor containing a series of static flow mixers. [Specific Example 43.] The integration method of Specific Example 41 further includes supplying a monosilaneamine precursor carried in the first and second carrier gases from the precursor generation chamber to the measurement chamber, so as to monitor and detect at least one parameter before supplying the monosilaneamine precursor carried in the first and second carrier gases to the thin film processing chamber. [Specific Example 44.] An integration method for forming metal halide precursors is based on pulse formation that is timed to match the pulse requirements of atomic layer deposition (ALD).

[0094] Those skilled in the art to which this application pertains will understand that the above-described embodiments can be modified without departing from the general inventive concept. Therefore, it should be understood that the present invention is not limited to the specific embodiments disclosed, but is intended to include modifications within the spirit and scope of the invention as defined by the appended claims.

[0095] 100: Integrated System 101: Precursor Formation Chamber 102: Processing Room 103: Valve assembly 104: Source of raw materials 105: First catheter 106: Raw material entry 107: Precursor Export 108: Second catheter 109: Facilities 110: manifold 201: Precursor Synthesis Chamber 202: Thin Film Processing Room 203: Flushing Gas System 204: Various institutions and controls 205: Emission System 206: Manifold System 207: Conduit or tubing 301: Precursor Synthesis Chamber 302: Thin Film Processing Room 303: Solvent System 304: Flushing System 305: Various instruments and controls 306: Manifold System 307: Pipelines 308: Emission System 309: Solvent waste liquid 401: Wafer Handling System 402: Storage Box 403: Thin Film Processing Room 404a,b,c: Precursor synthesis chamber 501: Wafer Handling System 502: Robotic Arm 503: Storage Box 504a,b: Precursor Synthesis Chamber 505a,b: Thin Film Processing Chamber 506: Metrology Room 601: Storage Box 602a,b,c,d,e: Thin film processing chamber 603a,b,c,d,e: Precursor synthesis chamber 604: Processing Chamber Sensor 605: Chemical Generator Sensor 606: Function Block 607: Chemical Generator Controller 608: Robotic Arm 609: Washer 701: Raw material rolls for flexible substrates 702: End Roller 703a,b: Processing Room 704: Intermediate Room 705a,b: Precursor Synthesis Chamber 706a,b: Process controller 707a,b: Measuring instruments 708: Measuring Instruments 709a,b: Converter processing modes 710a,b: Preset machining setting points 711a,b: Lines or conduits

Claims

1. An integrated method for synthesizing a film formation precursor, consuming the precursor, and forming a thin film on a substrate, the method comprising: providing a raw material source containing at least one raw material at a first location; supplying at least one raw material from the raw material source to a precursor synthesis chamber at the first location; reacting at least one raw material in the precursor synthesis chamber to form a precursor at the first location; supplying the precursor from the precursor synthesis chamber to a thin film processing chamber at the first location in a controlled manner, the thin film processing chamber operating in parallel with and directly connected to the precursor synthesis chamber; and using a manufacturing technique to consume the precursor to form a thin film on a substrate located in the thin film processing chamber at the first location; The endpoint is used for real-time monitoring and detection of at least one parameter selected from the group consisting of: processing parameters of the precursor synthesis chamber, processing parameters of the thin film processing chamber, parameters of reaction byproducts and effluents, and at least one property of the thin film; and feedback regarding precursor consumption and thin film formation is transmitted to the precursor synthesis chamber to control the synthesis of the precursor such that (i) the synthesis of the precursor and the formation of the thin film occur simultaneously or in conjunction, (ii) the rate of precursor synthesis is matched with the requirements of precursor consumption and thin film formation, and (iii) the rate of precursor synthesis is synchronized with the rate of precursor consumption for forming the thin film.

2. The integration method of claim 1 further includes comparing the amount or concentration of precursor entering the thin film processing chamber with the amount or concentration of precursor leaving the precursor synthesis chamber to calculate the difference, and using the difference as part of an algorithm to control the precursor synthesis rate in the precursor synthesis chamber.

3. The integration method of claim 1, wherein the manufacturing technology is selected from the group consisting of chemical vapor deposition (CVD), atomic layer deposition (ALD), liquid phase plating, etching, atomic layer etching, ion implantation and patterning.

4. The integration method of claim 1, wherein the supply of the precursor from the precursor synthesis chamber to the thin film processing chamber is carried out by using at least one of vacuum, inert gas, hydrogen, reactive gas, or a combination of inert gas and hydrogen reactive gas.

5. The integration method of claim 1, wherein the precursor system is delivered to the thin film processing chamber using an inert or reactive carrier gas.

6. The integration method of claim 1, wherein the precursor is volatilized or evaporated and transported to the thin film processing chamber using its own vapor pressure.

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