JP4960720B2 - Membrane precursor trays used in membrane precursor evaporation systems and methods of use thereof - Google Patents

Description

  The present invention relates to a system for forming a thin film, and more particularly to a system for evaporating a film precursor and supplying a vapor phase to a film forming chamber.

  This application is a continuation-in-part of each of the following US patent applications: 11/007961 filed in September 2004, 11/007965 filed in September 2004, November 29, 2004. No. 10/998420 filed on the day. All of these are specifically incorporated as references in this application.

  U.S. Patent Application No. 11/007961 is a continuation-in-part of U.S. Patent Application No. 10/998420 filed on November 29, 2004, and U.S. Patent Application No. 11/007962 is filed on Nov. 2004. This is a continuation-in-part of US patent application Ser. No. 10/998420 filed on 29th, all of which are specifically incorporated by reference in this application.

  This application is related to US patent application Ser. No. 11 / 351,539, entitled “Thin Film Precursor Deposition System and Method of Use thereof,” filed on the same day as express delivery EV 488818447 US, which is incorporated herein by reference. It has been clearly incorporated as.

  When installing copper (Cu) metal in a multi-layer metallized structure to produce an integrated circuit, a diffusion barrier / liner is used to improve Cu layer adhesion and growth, leading to a Cu dielectric material It is necessary to prevent the diffusion of The barrier / liner deposited on the dielectric material may comprise a refractive material that is non-reactive and immiscible with Cu, such as tungsten (W), molybdenum (Mo), and tantalum (Ta). Well, this can reduce the electrical resistance. Current integrated structures that integrate metallized Cu and dielectric materials require a barrier / liner deposition process at substrate temperatures between about 400 ° C. and about 500 ° C. or lower.

  For example, in the current Cu integration method for node technology of 130 nm or less, a low dielectric constant (low k) interlayer dielectric is used, and then a TaN layer and a Ta barrier layer are formed by physical vapor deposition (PVD). In addition, a Cu seed layer is deposited by PVD, and an electrochemical deposition (ECD) Cu fill is installed. In general, Ta layers are selected by their adhesion (ie, their adhesion to low-k films), and generally Ta / TaN layers are their barrier properties (ie, diffusion of Cu into low-k films). Their protection against).

  As mentioned above, intensive efforts have been made to study and implement thin film transition metal layers such as Cu diffusion barriers, and these studies include materials such as chromium, tantalum, molybdenum and tungsten. It is. Each of these materials exhibits low miscibility with Cu. Recently, other materials such as ruthenium (Ru) and rhodium (Rh) have been found as potential barrier layers. This is because these materials are expected to exhibit the same behavior as conventional heat-resistant materials.

  In the present invention, a highly conductive multi-tray film precursor evaporation system coupled to a highly conductive gas phase supply system (40) to increase the deposition rate by increasing the exposed surface area of the film precursor. It is an issue to provide.

  In one embodiment of the present invention, a system for depositing a thin film from a film precursor is provided.

  In another embodiment of the present invention, a film precursor evaporation system is provided.

  In yet another embodiment of the present invention, a method and system for depositing a metal film from a solid metal precursor at high speed is provided.

  In yet another embodiment, a replaceable membrane precursor support assembly is proposed, which supports the membrane precursor in a membrane precursor evaporation system and includes one or more additional stackable layers. The film precursor evaporation system includes a container having an outer wall and a bottom, and a lid configured to be hermetically coupled to the container. The lid has an outlet configured to hermetically couple with the thin film deposition system, and the replaceable tray has an inner end and an outer end, between the two, A film precursor is held, one of the ends is stackable, has one or more tray openings formed in the stackable end, and the replaceable tray is a carrier gas supply From the system towards the other end, the carrier gas Is configured to flow at the top, the carrier gas, together with film precursor vapor, it is exhausted through the outlet of the lid.

  In some embodiments of the present invention, the replaceable tray has an inner end and an outer end, the membrane precursor is held between the two, and the replaceable tray It has one or more tray openings formed at the inner end where stacking is possible, and the carrier gas flows from the carrier gas supply system toward the other end of the tray so as to flow above the film precursor. The carrier gas is exhausted through the outlet of the lid together with the film precursor gas phase.

  The following description is for explanation to better understand the present invention, and is not intended to limit the present invention. Specific details of the specific shape, various components, etc. of the film forming system are shown. Is. However, it should be noted that the present invention may be practiced in other embodiments that depart from these specific details.

  Referring to the drawings, like or corresponding parts are designated by like reference numerals throughout the several views. FIG. 1 illustrates a system 1 for depositing a thin film, such as a metal film, on a substrate according to one embodiment. The film forming system 1 includes a process chamber 10 having a substrate holder 20 configured to support a substrate 25, and a thin film is formed on the substrate 25. The process chamber 10 is coupled to a film precursor evaporation system 50 via a gas phase precursor supply system 40.

  Further, the process chamber 10 is coupled to a vacuum pump system 38 via a duct 36, which pumps the process chamber 10, vapor phase precursor supply system 40, and film precursor evaporation system 50 onto the substrate 25. The film is vacuum processed to a pressure suitable for forming a thin film on the substrate, and further to a pressure suitable for vaporizing a film precursor (not shown) in the film precursor evaporation system 50.

Referring to FIG. 1, a film precursor evaporation system 50 is configured to store a film precursor and to heat the film precursor to a temperature sufficient for the film precursor to volatilize, and the gas phase The film precursor is introduced into the gas phase precursor supply system 40. Hereinafter, the details will be described with reference to FIGS. 3 to 9, and the film precursor includes, for example, a solid film precursor. The film precursor may include, for example, a solid metal precursor. The film precursor may contain, for example, a carbonyl genus. For example, the carbonyl metal may include carbonyl ruthenium (Ru ₃ (CO) ₁₂ ) or carbonyl rhenium (Re ₂ (CO) ₁₀ ). The carbonyl metal may additionally include, for example, W (CO) ₆ , Mo (CO) ₆ , Co ₂ (CO) ₈ , Rh ₄ (CO) ₁₂ , Cr (CO) ₆ or Os (CO) _12. . In the case of forming tantalum (Ta), for example, the film precursors include TaF ₅ , TaCl ₅ , TaBr ₅ , TaI ₅ , Ta (CO) ₅ , Ta [N (C ₂ H ₅ CH ₃ )]. ₅ (PEMAT), Ta [N (CH ₃ ) ₂ ] ₅ (PDMAT), Ta [N (C ₂ H ₅ ) ₂ ] ₅ (PDEAT), Ta (NC (CH ₃ ) ₃ ) (N (C ₂ H ₅ ) ₂ ) ₃ (TBTDET), Ta (NC ₂ H ₅ ) (N (C ₂ H ₅ ) ₂ ) ₃ , Ta (NC (CH ₃ ) ₂ C ₂ H ₅ ) (N (CH ₃ ) ₂ ) ₃ , Ta (NC (CH ₃ ) ₃ ) (N (CH ₃ ) ₂ ) ₃ or Ta (EtCp) ₂ (CO) H. For example, when titanium (Ti) is formed, the film precursors are TiF ₄ , TiCl ₄ , TiBr ₄ , TiI ₄ , Ti [N (C ₂ H ₅ CH ₃ )] ₄ (TEMAT), Ti [ N (CH ₃ ) ₂ ] ₄ (TDMAT), Ti [N (C ₂ H ₅ ) ₂ ] ₄ (TDEAT) may be included. When depositing ruthenium (Ru), for example, the film precursors are Ru (C ₅ H ₅ ) ₂ , Ru (C ₂ H ₅ C ₅ H ₄ ) ₂ , Ru (C ₃ H ₇ C ₅ H ₄ ) ₂ , Ru (CH ₃ C ₅ H ₄ ) ₂ , Ru ₃ (CO) ₁₂ , C ₅ H ₄ Ru (CO) ₃ , RuCl ₃ , Ru (C ₁₁ H ₁₉ O ₂ ) ₃ , Ru (C ₈ H ₁₃ O ₂ ) ₃ or Ru (C ₅ H ₇ O) ₃ may be included.

To obtain the desired temperature for volatilizing the film precursor (or sublimating the solid metal precursor), the film precursor evaporation system 50 is coupled to an evaporation temperature control system 54 configured to control the evaporation temperature. . For example, in a conventional system, the temperature of the film precursor is usually raised to about 40 ° C. or more, and the film precursor is sublimated or evaporated. When the film precursor is heated and evaporation (or sublimation) occurs, the carrier gas is carried over or by the film precursor. The carrier gas is, for example, an inert gas such as a noble gas (ie, He, Ne, Ar, Kr, Xe), or a monoxide such as carbon monoxide (CO) used with a carbonyl metal, or A mixture thereof may also be included. For example, the carrier gas supply system 60 is coupled to the film precursor evaporation system 50, which is configured to supply a carrier gas to the top of the film precursor, for example, via a supply line 61. In another example, the carrier gas supply system 60 is coupled to the gas phase precursor supply system 40 and is configured to supply the carrier gas to the gas phase of the film precursor via the supply line 63, thereby or Thereafter, the film precursor is introduced into the vapor phase precursor supply system 40. Although not shown in the figure, the carrier gas supply system 60 includes a gas source, one or more control valves, one or more filters, and a mass flow controller. For example, the flow rate of the carrier gas ranges from about 5 sccm (standard cm ³ / min) to about 1000 sccm. In another example, the carrier gas flow rate may range from about 20 seem to about 100 seem.

  Downstream of the film precursor evaporation system 50, the gas phase of the film precursor flows with the carrier gas via the gas phase precursor supply system 40, which is a gas phase dispersion system coupled to the process chamber 10. 30. The gas phase precursor supply system 40 is coupled to the gas phase line temperature control system 42 to control the temperature of the gas phase line, preventing the gas phase decomposition of the film precursor and the concentration of the film precursor gas phase. . For example, the gas phase line temperature is set to a value approximately equal to or higher than the evaporation temperature. Also, for example, the vapor phase precursor delivery system 40 may be characterized to have a high conductivity in excess of about 50 liters / second.

  Referring again to FIG. 1, the gas phase dispersion system 30 coupled to the process chamber 10 has a plenum 32 in which the gas phase is dispersed before penetrating the gas phase dispersion plate 34 and the substrate 25 Introduced into the upper processing zone. The vapor dispersion plate 34 is also coupled to a dispersion plate temperature control system 35 that is configured to control the temperature of the vapor dispersion plate 34. For example, the temperature of the gas phase dispersion plate is set to a value substantially equal to the gas phase line temperature. However, this temperature may be lower or higher.

  Once the film precursor gas phase is introduced into the processing zone 33, the film precursor gas phase is thermally decomposed when adsorbed on the substrate surface because the temperature of the substrate 25 is high, and a thin film is formed on the substrate 25. Is formed. The substrate holder 20 is coupled to the substrate temperature control system 22 and is configured to raise the temperature of the substrate 25. For example, the substrate temperature control system 22 is configured to raise the temperature of the substrate 25 to about 500 ° C. In some embodiments, the substrate temperature ranges from about 100 ° C to about 500 ° C. In another example, the substrate temperature ranges from about 300 ° C to about 400 ° C. The process chamber 10 may also be coupled to a chamber temperature control system 12 configured to control the temperature of the chamber walls.

  As described above, for example, the conventional system may be coupled to the film precursor vapor system 50 and the vapor phase at a temperature of about 40 ° C. or higher in order to suppress decomposition of the metal vapor precursor and concentration of the metal vapor precursor. The precursor supply system 40 is activated.

  Further, it is preferable that the film forming system 1 is periodically cleaned before processing of one or more substrates is performed. For example, additional details of cleaning methods and systems can be found in a co-pending US patent entitled “Method and System for Performing In-Situ Cleaning of Deposition Systems” filed Nov. 29, 2004. Application No. 10/998394. This is incorporated as a reference for this application.

  As mentioned above, the deposition rate is proportional to the amount of film precursor that has been transported to the substrate before it evaporates and decomposes, concentrates, or both. Therefore, in order to obtain a desired film formation rate from one substrate to the next substrate and maintain certain processing characteristics (that is, film formation rate, film thickness, film uniformity, film properties, etc.) It is important to provide the ability to monitor, regulate or control the flow rate of the film precursor gas phase. In conventional systems, the operator has indirectly determined the flow rate of the film precursor gas phase using the evaporation temperature and a predetermined relationship between the evaporation temperature and the flow rate. However, it is inevitable that the flow rate is measured more accurately in order to perform processing at an appropriate time and obtain characteristics. For example, additional details can be found in copending US patent application Ser. No. 10 / 998,393, filed Nov. 29, 2004, entitled “Method and System for Measuring Flow Rate in a Solid Precursor Delivery System”. Is shown in This is incorporated as a reference for this application.

  Referring to FIG. 1 again, the film forming system 1 further includes a control system 80, which is configured to operate the film forming system 1 and control its operation. The control system 80 includes a process chamber 10, a substrate holder 20, a substrate temperature control system 22, a chamber temperature control system 12, a gas phase dispersion system 30, a gas phase precursor supply system 40, a film precursor evaporation system 50, and a carrier gas supply system. 60.

  As yet another embodiment, FIG. 2 shows a film forming system 100 for forming a thin film such as a metal film on a substrate. The film forming system 100 includes a process chamber, and the process chamber includes a substrate holder 120 configured to support a substrate 125 on which a thin film is formed. The process chamber 110 stores a film precursor (not shown) and vaporizes a film precursor evaporation system 150; a gas phase precursor supply system 140 configured to transport the film precursor gas phase; Is coupled to a precursor delivery system 105.

  The process chamber 110 has an upper chamber section 111, a bottom chamber section 112, and an exhaust chamber 113. An opening 114 is formed in the bottom chamber section 112, and the bottom section 112 is coupled to the exhaust chamber 113.

  Referring to FIG. 2 again, the substrate holder 120 provides a horizontal surface to the processing target substrate (or wafer) 125. The substrate holder 120 is supported by a cylindrical support member 122, which extends upward from the bottom of the exhaust chamber 113. If necessary, a guide ring 124 for positioning the substrate 125 on the substrate holder 120 is installed at the end of the substrate holder 120. The substrate holder 120 also includes a heater 126 that is coupled to the substrate holder temperature control system 128. The heater 126 may include, for example, one or more resistance heating elements. Alternatively, the heater 126 may include a radiant heating element such as a tungsten halogen lamp. The substrate holder temperature control system 128 includes a power source that supplies power to one or more heating elements, one or more temperature sensors that measure the substrate temperature and / or substrate holder temperature, and the temperature of the substrate or substrate holder. And a controller configured to perform at least one of monitoring, adjustment or control.

During the treatment process, the heated substrate 125 thermally decomposes the gas phase of the film precursor gas phase such as the metal-containing film precursor to form a thin film such as a metal layer on the substrate 125. Is possible. In some embodiments, the film precursor includes a solid precursor. In another example, the film precursor includes a metal precursor. In another example, the film precursor comprises a solid metal precursor. In yet another embodiment, the film precursor includes a carbonyl metal precursor. In yet another embodiment, the film precursor comprises a carbonyl ruthenium precursor, such as Ru ₃ (CO) ₁₂ . In yet another embodiment of the invention, the film precursor comprises a carbonyl rhenium precursor, such as Re ₂ (CO) ₁₀ . It will be apparent to those skilled in the art of thermal chemical vapor deposition that other carbonyl ruthenium and carbonyl rhenium precursors can be used without departing from the scope of the present invention. In yet another embodiment, the film precursor is W (CO) ₆ , Mo (CO) ₆ , Co ₂ (CO) ₈ , Rh ₄ (CO) ₁₂ , Cr (CO) ₆ or Os (CO) ₁₂ . is there. For example, when tantalum (Ta) is formed, the film precursors are TaF ₅ , TaCl ₅ , TaBr ₅ , TaI ₅ , Ta (CO) ₅ , Ta [N (C ₂ H ₅ CH ₃ )] _5. (PEMAT), Ta [N (C ₂ H ₅ CH ₃ )] ₅ (PEMAT), Ta [N (CH ₃ ) ₂ ] ₅ (PDMAT), Ta [N (C ₂ H ₅ ) ₂ ] ₅ (PDEAT) , Ta (NC (CH ₃ ) ₃ ) (N (C ₂ H ₅ ) ₂ ) ₃ (TBTDET), Ta (NC ₂ H ₅ ) (N (C ₂ H ₅ ) ₂ ) ₃ , Ta (NC (CH ₃ ) ₂ C ₂ H ₅ ) (N (CH ₃ ) ₂ ) ₃ , Ta (NC (CH ₃ ) ₃ ) (N (CH ₃ ) ₂ ) ₃ or Ta (EtCp) ₂ (CO) H. For example, when titanium (Ti) is formed, the film precursors are TiF ₄ , TiCl ₄ , TiBr ₄ , TiI ₄ , Ti [N (C ₂ H ₅ CH ₃ )] ₄ (TEMAT), Ti [ N (CH ₃ ) ₂ ] ₄ (TDMAT), Ti [N (C ₂ H ₅ ) ₂ ] ₄ (TDEAT) may be included. For example, when ruthenium (Ru) is deposited, the film precursors are Ru (C ₅ H ₅ ) ₂ , Ru (C ₂ H ₅ C ₅ H ₄ ) ₂ , Ru (C ₃ H ₇ C ₅ H ₄ ) ₂ , Ru (CH ₃ C ₅ H ₄ ) ₂ , Ru ₃ (CO) ₁₂ , C ₅ H ₄ Ru (CO) ₃ , RuCl ₃ , Ru (C ₁₁ H ₁₉ O ₂ ) ₃ , Ru (C ₈ H ₁₃ O ₂ ) ₃ or Ru (C ₅ H ₇ O) ₃ may also be included.

  For example, the substrate holder 120 is heated to a predetermined temperature suitable for forming a desired metal layer on the substrate 125. A heater (not shown) is coupled to the chamber temperature control system 121 and embedded in the wall of the process chamber 110, thereby heating the chamber wall to a predetermined temperature. The heater is maintained such that the temperature of the walls of the process chamber 110 is in the range of about 40 ° C. to about 100 ° C., such as about 40 ° C. to about 80 ° C. A pressure gauge (not shown) is used to measure the pressure in the process chamber.

  As also shown in FIG. 2, the gas phase dispersion system 130 is coupled to the upper chamber section 111 of the process chamber 110. The gas phase dispersion system 130 includes a gas phase dispersion plate 131 that processes the precursor gas phase from the gas phase dispersion plenum 132 through one or more orifices 134 on top of the substrate 125. It is configured to be introduced into the zone 133.

  Further, an opening 135 is formed in the upper chamber section 111 for introducing the gas phase precursor from the gas phase precursor supply system 140 into the gas phase dispersion plenum 132. In addition, a temperature control element 136, such as a concentric fluid groove configured to supply a cooling fluid or a heating fluid, is provided to control the temperature of the gas phase dispersion system 130. Degradation of the film precursor in the phase dispersion system 130 is avoided. For example, a fluid such as water is supplied from the gas phase dispersion temperature control system 138 to the fluid channel. The gas phase dispersion temperature control system 138 includes a fluid source, a heat exchanger, one or more temperature sensors that measure the fluid temperature and / or the temperature of the gas phase dispersion plate, and the temperature of the gas phase dispersion plate 131. And a controller configured to control from about 20 ° C to about 100 ° C.

  The film precursor evaporation system 150 is configured to hold the film precursor and raise the temperature of the film precursor to volatilize (or sublimate) the film precursor. A precursor heater 154 is installed to heat the film precursor and maintain the film precursor at a temperature that provides the desired gas phase pressure. Precursor heater 154 is coupled to an evaporation temperature control system 156, which is configured to control the temperature of the film precursor. For example, the precursor heater 154 is configured to adjust the temperature (or evaporation temperature) of the film precursor to about 40 ° C. or higher. Alternatively, the evaporation temperature may be raised to about 50 ° C. or higher. For example, the evaporation temperature is raised to a temperature of about 60 ° C. or higher. In one embodiment, the evaporation temperature is raised to a range of about 60-100 ° C, and in another embodiment, the evaporation temperature is raised to a range of about 60-90 ° C. Further, the precursor heater may be provided for each tray. Such a heater may be, for example, a resistance heating type.

As the film precursor is heated, evaporation (or sublimation) occurs and the carrier gas passes over or is transported by the film precursor. The carrier gas is, for example, an inert gas such as a noble gas (ie, He, Ne, Ar, Kr, Xe), or a monoxide such as carbon monoxide (CO) used with a carbonyl metal, or these A mixture of For example, the carrier gas supply system 160 is coupled to the film precursor evaporation system 150, which is configured, for example, to supply a carrier gas on top of the film precursor. Although not shown in FIG. 2, the carrier gas supply system 160 is coupled to the vapor phase precursor supply system 140 to supply the carrier gas into the gas phase of the film precursor, thereby or after that. The gas phase is introduced into the gas phase precursor supply system 140. The carrier gas supply system 160 includes a gas source 161, one or more control valves 162, one or more filters 164, and a mass flow controller 165. For example, the flow rate of the carrier gas ranges from about 5 sccm (standard cm ³ / min) to about 1000 sccm. In certain embodiments, for example, the carrier gas flow rate ranges from about 10 seem to about 200 seem. In another example, for example, the flow rate of the carrier gas ranges from about 20 sccm to about 100 sccm.

  A sensor 166 is also installed that measures the total gas flux from the film precursor evaporation system 150. The sensor 166 includes, for example, a mass flow controller, and the amount of film precursor supplied to the process chamber 110 is determined using the sensor 166 and the mass flow controller 165. Alternatively, the sensor 166 may comprise a light absorption sensor, in which case the concentration of the film precursor in the gas flux towards the process chamber 110 is measured.

  A bypass line 167 may be installed downstream of the sensor 166 and connects the gas phase supply system 140 to the exhaust line 116. A bypass line 167 is provided to vacuum process the vapor phase precursor supply system 140 and stabilize the supply of film precursor to the process chamber 110. A bypass line 168 is installed in the bypass line 167 downstream from the branch of the vapor phase precursor supply system 140.

  Referring also to FIG. 2, the vapor phase precursor supply system 140 has a highly conductive vapor line, which has first and second valves 141, 142. The gas phase precursor supply system 140 further includes a gas phase line temperature control system 143. The gas phase line temperature control system 143 uses a heater (not shown) for the gas phase precursor supply system 140. It is configured to heat. The temperature of the gas phase line is controlled to avoid concentration of the film precursor in the gas phase line. The temperature of the gas phase line is controlled from about 20 ° C. to about 100 ° C. or from about 40 ° C. to about 90 ° C. For example, the gas phase line temperature is set to a value approximately equal to or greater than the evaporation temperature.

Further, the dilution gas may be supplied from the dilution gas supply system 190. The diluent gas is, for example, an inert gas such as a noble gas (ie, He, Ne, Ar, Kr, Xe), or a monoxide such as carbon monoxide (CO) used with a carbonyl metal, or these May also be included. For example, the dilution gas supply system 190 is coupled to the vapor phase precursor supply system 140, which is configured to supply dilution gas to the vapor phase film precursor, for example. The dilution gas supply system 190 includes a gas source 191, one or more control valves 192, one or more filters 194, and a mass flow controller 195. For example, the flow rate of the carrier gas ranges from about 5 sccm (standard cm ³ / min) to about 1000 sccm.

  The mass flow controllers 165 and 195 and valves 162, 192, 168, 141 and 142 are controlled by a controller 196, which controls supply, shut-off, carrier gas, film precursor gas phase and dilution gas. To control the flux. A sensor 166 is further connected to the controller 196, and based on the output of the sensor 166, the controller 196 controls the carrier gas flux via the mass flow controller 165, thereby controlling the process chamber 110. Thus, a desired film precursor flux is obtained.

  As shown in FIG. 2, the exhaust line 116 connects the exhaust chamber 113 with the pump system 118. Using the vacuum pump 119, the process chamber 110 is vacuum processed to the desired vacuum stage, and gas species are removed from the process chamber 110 during the processing process. An automatic pressure controller (APC) 115 and a trap 117 may be used in series with the vacuum pump 119. The vacuum pump 119 may include a turbo molecular pump (TMP) with a pump speed of 5000 liters / second (and higher). Alternatively, the vacuum pump 119 may include a dry roughing pump. During the processing process, carrier gas, diluent gas, film precursor gas phase, or combinations thereof are introduced into the process chamber 110 and the chamber pressure is adjusted by the APC 115. For example, the chamber pressure ranges from about 1 mTorr to about 500 mTorr, and in another example, the chamber pressure ranges from about 5 mTorr to 50 mTorr. The APC 115 may have a butterfly type valve or a gate valve. Trap 117 collects unreacted precursor material and by-products from process chamber 110.

  Referring to the substrate holder 120 in the process chamber 110, as shown in FIG. 2, three substrate lift pins 127 (only two are shown) are installed to hold, raise and lower the substrate 125. . The substrate lift pins 127 are coupled to the plate 123 and can be lowered below the upper surface of the substrate holder 120. For example, means for raising and lowering the plate 123 using a drive mechanism 129 such as an air cylinder is provided. The substrate 125 is transferred into and out of the process chamber 110 by a robot transfer system (not shown) via the gate valve 200 and the chamber through passage 202, and the substrate 125 is received by the substrate lift pins 127. Once the substrate 125 is received in the transport system, the substrate is lowered onto the upper surface of the substrate holder 120 by lowering the substrate lift pins 127.

  Referring to FIG. 2, the controller 180 has a microprocessor, memory, and digital I / O port and communicates with and operates the input of the processing system 100 and outputs from the processing system 100. Generate enough control voltage to monitor. The processing system controller 180 also includes a process chamber 110; a precursor supply system 105 having a controller 196, a gas phase line temperature control system 142 and an evaporation temperature control system 156; a gas phase dispersion temperature control system 138; a vacuum pump system 118. As well as the substrate holder temperature control system 128; to exchange information. In the vacuum pump system 118, a controller 180 is coupled with an automatic pressure controller 115 that controls the pressure in the process chamber 110 to exchange information. Using the program stored in the memory, the aforementioned components of the film forming system 100 are controlled based on the stored process recipe. An example of a processing system controller 180 is a Del Precision workstation 610, which is available from Dallas Dell Corporation, Texas. The controller 180 may be operated by a general purpose computer, a digital signal processor, or the like.

  However, the controller 180 is responsive to a processor running on a general purpose computer system and executing one or more sequences of instructions stored in memory, and based on the process steps of the present invention, Part or all may be implemented. Such instructions may be read in the control memory from another computer readable medium such as a hard disk or a removable media drive. Alternatively, one or more processors in a multi-process arrangement may be used as a control microprocessor to execute a series of instructions stored in main memory. In another embodiment, hard wire circuitry may be used instead of or in combination with software instructions. Thus, embodiments are not limited to any specific combination of hardware circuitry and software.

  Controller 180 has at least one computer readable medium, or memory such as control memory, holds programmed instructions according to the present invention, and data structures, tables, records or other data necessary to implement the present invention. To accommodate. Examples of computer readable media are compact disk, hard disk, floppy disk, tape, magneto-optical disk, PROM (EPROM, EEPROM, flash EPROM), DRAM, SRAM, SDRAM, or any other magnetic medium, compact disk (Eg CD-ROM) or any other optical medium, punch card, paper tape, or other physical medium with a hole pattern, carrier wave (shown below), or any other medium that can be read by a computer May be.

  When stored on any one or a combination of computer-readable media, the present invention may include software that controls controller 180, software that drives a device or device that implements the present invention, and / or a human user. Includes software to obtain a controller to exchange information. Such software includes, but is not limited to, device drivers, operating systems, development tools, and application software. Such computer-readable media further includes a computer program product that performs some or all of the processing (if a processing process is assigned) for performing the present invention.

  The computer code apparatus of the present invention may be any interpretable or executable code mechanism, including but not limited to interpretable programs, dynamic ink libraries (DLLs), Java classes, and A complete execution program may be included. Also, some of the processes of the present invention may be provided with better characteristics, reliability and / or cost.

  In this application, the term “computer-readable medium” is used to refer to any medium that provides instructions to the processor of controller 180 when instructed. Computer-readable media is in many forms, including but not limited to, non-volatile media, volatile media, and transmission media. Non-volatile media includes, for example, optical disks, magnetic disks, and magneto-optical disks, such as hard disks or removable media drives. Volatile media includes dynamic memory, such as main memory. Various forms of computer readable media include those that, when executed, carry one or more sequences of instructions to a controller processor. For example, the instructions are initially carried on the magnetic disk of the remote computer. The remote computer loads the instructions, remotely executes all or part of the present invention in dynamic memory, and sends the instructions to the controller 180 via the network.

  The controller 180 may be installed in the vicinity of the film forming system 100, or may be installed remotely in the film forming system 100 via the Internet or an intranet. Therefore, the controller 180 can exchange data with the film forming system 100 using at least one of a direct connection, an intranet, and the Internet. The controller 180 may be coupled to the intranet at the customer site (ie, device manufacturer side) or may be coupled to the intranet at the vendor site (ie, device manufacturer side). Another computer (ie, controller, server, etc.) may access controller 180 to exchange data via at least one of a direct connection, an intranet, or the internet.

  Reference is now made to FIG. 3, which shows a cross-sectional view of a film precursor evaporation system 300 according to an embodiment. The film precursor evaporation system 300 includes a container 310 having an outer wall 312 and a bottom 314. The film precursor evaporation system 300 includes a lid 320 configured to be hermetically bonded to the container 310. The lid 320 is hermetically bonded to a thin film deposition system as illustrated in FIG. The outlet 322 is configured as described above. The container 310 and the lid 320 constitute a sealed environment when joined to the thin film deposition system. The container 310 and the lid 320 are made of, for example, A6061 aluminum, and may or may not be coated thereon.

  In addition, the container 310 is coupled to a heater (not shown) to increase the evaporation temperature of the film precursor evaporation system 300, and at least one of monitoring, adjusting, or controlling the evaporation temperature is performed. It is configured to be coupled to a temperature control system (not shown). When the evaporation temperature reaches an appropriate value as described above, the film precursor evaporates (or sublimates) to form a film precursor gas phase, which passes through the vapor supply system, and the thin film deposition system. To be transported. The container 310 is hermetically joined to a carrier gas supply system (not shown), and the container 310 is configured to receive a carrier gas that conveys the film precursor gas phase.

  Referring to FIGS. 3 and 4, the film precursor evaporation system 300 further includes a base tray 330, which is formed on the bottom 314 of the container 310, and the film precursor 350 on the base tray 330 is It has a base outer wall 332 configured to hold. The base outer wall 332 has a base support end where the upper tray is supported as shown below. The base outer wall 332 also has one or more base tray openings 334 that extend from a carrier gas supply system (not shown) to the top of the membrane precursor 350 toward the center of the vessel 310. The carrier gas is configured to flow, and the carrier gas is discharged from the outlet 322 of the lid 320 together with the film precursor gas phase along the gas phase exhaust space such as the central groove 318. For this reason, the level of the film precursor in the base tray 330 is set below the position of the base tray opening 334.

  Referring to FIGS. 3 and 5A, 5B, the film precursor evaporation system 300 further includes one or more stackable upper trays 340 that support the film precursor 350 and at least It is configured to be installed or stacked on one base tray 330 or another stackable upper tray 340. Each stackable upper tray 340 has an upper outer wall 342 and an inner wall 344, and is configured so that the film precursor 150 is held therebetween. Inner wall 344 defines a central flux groove 318. The upper outer wall 342 also has an upper support end 333 that supports an additional upper tray 340. Accordingly, the first upper tray 340 is installed so as to be held by the base support end 333 of the base tray 330, and if necessary, one or more additional upper trays can be attached to the upper tray 340 of the previous stage. You may install so that it may be supported by the upper support edge part 343. FIG. The upper outer wall 342 of each upper tray 340 has one or more upper tray openings 346 that pass from a carrier gas supply system (not shown) through the central flux groove 318 of the container 310. The carrier gas is configured to flow over the film precursor 350, and the carrier gas is exhausted through the outlet 322 of the lid 320 together with the gas phase of the film precursor. For this reason, the inner wall 344 needs to be shorter than the upper outer wall 342, so that the carrier gas can flow substantially radially toward the central flux groove 318. Further, the level of the film precursor in each upper tray 340 needs to be lower than the height of the inner wall 342 and lower than the position of the upper tray opening 346.

  The upper tray 340 that can be stacked with the base tray 330 is drawn in a cylindrical shape. However, this shape may be changed. For example, the tray shape may be rectangular, square, or oval. Similarly, the inner wall 344 and even the central upper flux groove 318 may have different shapes.

  When one or more stackable trays 340 are stacked on the base tray 330, a stack 370 is formed, whereby the base tray 330 has a base outer wall 332 and a container outer wall 312 and one or more stacks. A peripheral groove-shaped carrier gas supply space such as an annular space 360 is provided between the upper outer wall of the possible upper tray 240 and the container outer wall 312. In addition, the container may have one or more spacers (not shown), which are the base outer wall 332 of the base tray 330 and the upper outer wall of the one or more stackable upper trays 340. 342 is separated from the container outer wall 312, thereby ensuring an equivalent space in the annular space 360. In another method of an embodiment, the container 310 is configured such that the base outer wall 332 and the top wall 342 are aligned vertically. Container 310 may also have one or more thermal contact members (not shown) that provide mechanical contact between the inner wall of container 310 and the outer wall of each tray. This facilitates the transfer of thermal energy from the wall of the container 310 to each tray.

  A sealing device such as an O-ring may be installed between each tray and adjacent trays, in which case a vacuum seal is obtained between one tray and the next. For example, the sealing device may be placed in a receiving groove (not shown) formed in the upper support end 343 of the upper outer wall 342 and the base support end 333 of the base outer wall 332. In this case, once the tray is introduced into the container 310, the sealing of each sealing device is facilitated by the joining of the lid 320 and the container 310. The sealing device may have an elastomer O-ring, for example. Further, the sealing device may include, for example, a VITON O-ring.

  The number of trays including both the base tray and the stackable upper tray ranges from 2 to 20, for example, in one embodiment, the number of trays is 5, as shown in FIG. In one embodiment, the stack 370 includes a base tray 330 and at least one upper tray 340 supported by the base tray 330. The base tray 330 may be the one shown in FIGS. 3 and 4 and may have the same configuration as the upper tray 340 shown in FIGS. 3 to 5B. In other words, the base tray 330 may have an inner wall. In FIGS. 3-5B, the stack 370 is shown as having a base tray 330 and one or more separate and stackable top trays 340, but the system 300 ′ is a container having a stack 370 ′. 310 ', this stack is a single integrated piece with one or more upper trays 340 and base tray 330 integrated, as shown in FIG. The outer wall 342 is integrated. The term integral includes monolithic structures such as monolithic structures that do not have a clear boundary between trays and mechanically bonded structures that are permanently in contact or have a permanent joint between the trays. I need to understand that. It should be understood that the term separable does not include a bonder or temporary bonder between trays, whether tight or mechanical.

Regardless of being stackable or integral, the base tray 330 and each upper tray 340 are configured to support the film precursor 350. In certain embodiments, film precursor 350 includes a solid precursor. In another example, the film precursor 350 has a liquid precursor. In another example, the film precursor 350 has a metal precursor. In another example, the film precursor 350 includes a solid metal precursor. In yet another example, the film precursor 350 includes a carbonyl metal precursor. In yet another example, the film precursor 350 comprises a carbonyl ruthenium precursor, such as Ru ₃ (CO) ₁₂ . In yet another example, the film precursor 350 comprises a carbonyl rhenium precursor, such as Re ₂ (CO) ₁₀ . In yet another embodiment, the film precursor 350 may be W (CO) ₆ , Mo (CO) ₆ , Co ₂ (CO) ₈ , Rh ₄ (CO) ₁₂ , Cr (CO) ₆ or Os (CO) _12. including. In yet another embodiment, when tantalum (Ta) is deposited, the film precursor 350 is TaF ₅ , TaCl ₅ , TaBr ₅ , TaI ₅ , Ta (CO) ₅ , Ta [N (C _2). H ₅ CH ₃ )] ₅ (PEMAT), Ta [N (CH ₃ ) ₂ ] ₅ (PDMAT), Ta [N (C ₂ H ₅ ) ₂ ] ₅ (PDEAT), Ta (NC (CH ₃ ) ₃ ) (N (C ₂ H ₅ ) ₂ ) ₃ (TBTDET), Ta (NC ₂ H ₅ ) (N (C ₂ H ₅ ) ₂ ) ₃ , Ta (NC (CH ₃ ) ₂ C ₂ H ₅ ) (N ( CH ₃ ) ₂ ) ₃ , Ta (NC (CH ₃ ) ₃ ) (N (CH ₃ ) ₂ ) ₃ or Ta (EtCp) ₂ (CO) H. In yet another embodiment, when titanium (Ti) is deposited, the film precursor 350 is TiF ₄ , TiCl ₄ , TiBr ₄ , TiI ₄ , Ti [N (C ₂ H ₅ CH ₃ )]. ₄ (TEMAT), Ti [N (CH ₃ ) ₂ ] ₄ (TDMAT), Ti [N (C ₂ H ₅ ) ₂ ] ₄ (TDEAT) may be included. In still another embodiment, when ruthenium (Ru) is deposited, the film precursor 350 is composed of Ru (C ₅ H ₅ ) ₂ , Ru (C ₂ H ₅ C ₅ H ₄ ) ₂ , Ru ( C ₃ H ₇ C ₅ H ₄ ) ₂ , Ru (CH ₃ C ₅ H ₄ ) ₂ , Ru ₃ (CO) ₁₂ , C ₅ H ₄ Ru (CO) ₃ , RuCl ₃ , Ru (C ₁₁ H ₁₉ O ₂ ) ₃ , Ru (C ₈ H ₁₃ O ₂ ) ₃ or Ru (C ₅ H ₇ O) ₃ .

  As described above, the film precursor 350 may include a solid precursor. The solid precursor may be in the form of a solid powder or one or more tablets. For example, one or more solid tablets are prepared in a number of processing processes, including a sintering process, a stamping process, a dipping process, a spin coating process, or any combination thereof. The solid tablet-like solid precursor may or may not be in close contact with the base tray 330 or the upper tray 340. For example, the refractory metal powder may be sintered at a temperature of 2000 ° C. to 2500 ° C. in a sintering furnace for vacuum and inert gas atmosphere. Alternatively, for example, the refractory metal powder may be dispersed in a fluid medium, distributed to the tray, and uniformly distributed on the tray surface using a spin coating process. The refractory metal spin coat is then thermally cured.

  As described above, the carrier gas is supplied to the container 310 from a carrier gas supply system (not shown). As shown in FIGS. 3 and 6, the carrier gas is supplied from the lid 320 to the container 310 through a gas supply line (not shown) hermetically joined to the lid 320. The gas supply line provides a gas channel 380 that extends downstream through the outer wall 312 of the container 310 and through the bottom 314 and opening of the container 310 to the annular space 360.

  Alternatively, as shown in FIG. 7, the carrier gas may be supplied to the container 310 of the film precursor evaporation system 400 via the opening 480 in the lid 320, in which case the gas is directly into the annular space 360. Supplied. Alternatively, as shown in FIG. 8, the carrier gas may be supplied to the vessel 310 of the film precursor evaporation system 500 via an opening 580 in the outer wall 312, in which case the gas is directly into the annular space 360. Supplied.

  Referring again to FIG. 3, the inner diameter of the container outer wall 312 is, for example, in the range of about 10 cm to about 100 cm, for example, in the range of about 15 cm to about 40 cm. For example, the inner diameter of the outer wall 312 may be 20 cm. The diameter of the outlet 322 and the inner diameter of the inner wall 344 of the upper tray 340 may be, for example, in the range of about 1 cm to 30 cm, for example, the outlet diameter and the inner wall diameter are in the range of about 5 to about 20 cm. For example, the exit diameter may be 10 cm. In addition, the outer diameter of the base tray 330 and each upper tray 340 ranges from about 75% to about 99% of the inner diameter of the outer wall 312 of the container 310. For example, the tray diameter is equal to the inner diameter of the outer wall 312 of the container 310. It is in the range of about 85% to 99%. For example, the diameter of the tray is 19.75 cm. In addition, the height of the base outer wall 332 of the base tray 330 and the upper outer wall 342 of each upper tray 340 is in the range of about 5 mm to about 50 mm. For example, each height is about 30 mm. Also, the height 344 of each inner wall ranges from about 10% to about 90% of the height of the upper outer wall 342. For example, the height of each inner wall ranges from about 2 mm to about 45, such as from about 10 mm to about 20 mm. For example, the height of each inner wall is about 12 mm.

  Referring again to FIG. 3, one or more base tray openings 334 and one or more upper tray openings 346 may have one or more grooves. Alternatively, one or more base tray openings 334 and one or more upper tray openings 346 may have one or more orifices. The diameter of each orifice is, for example, in the range of about 0.4 mm to about 2 mm. For example, the diameter of each orifice may be about 1 mm. In one embodiment, the diameter of the orifice and the width of the annular space 360 are selected such that the conductivity of the annular space 360 is sufficiently greater than the net conductivity of the orifice, so that the carrier gas throughout the annular space 360 is The distribution is kept substantially uniform. If the conductivity of the annular space 360 is sufficiently large compared to the net conductivity of the orifice, the carrier gas will flow uniformly over the film precursor 350 in each tray. Those skilled in the art of vacuum design use the principles of conventional vacuum technology, or mathematical simulations or experiments, or a combination of these, taking into account the fabrication, the dimensions of the annular space 360, the opening 346 of each tray. Design criteria for the diameter of each tray, the length of each tray opening, etc. can be defined. For example, if 72 1 mm DIA tray openings and 5 trays are used and the container 310 has a diameter of about 20 cm, the thickness of the annular space 360 is about 1.8 mm or more, for example 2.65 mm. be able to. For example, when 72 0.4 mm DIA tray openings and 5 trays are used and the container 310 has a diameter of about 20 cm, the thickness of the annular space 360 should be about 0.55 mm or more. Can do. Further, for example, when 72 1.6 mm DIA tray openings and 5 trays are used and the container 310 has a diameter of about 20 cm, the thickness of the annular space 360 should be about 3.5 mm or more. Can do. The number of orifices is, for example, in the range of about 2 to about 1000, and in another embodiment in the range of about 50 to about 100. For example, one or more base tray openings 334 may have 72 orifices with a diameter of 1 mm, and one or two stackable tray openings 346 may have 72 orifices with a diameter of 1 mm. good. In this case, the width of the annular space 360 is about 2.65 mm.

  Further, the gas phase exhaust space, that is, the central flux groove 318 may be designed to have high flux conductivity. For example, the net flux conductivity from the outlet of one or two tray openings to the outlet 322 of the container 310 is greater than about 50 liters / second, or the flux conductivity is greater than about 100 liters / second, or The flux conductivity is greater than about 500 liters / second.

  Referring to FIG. 9, there is shown a cross-sectional view of a film precursor evaporation system 600 according to another embodiment. The film precursor evaporation system 600 has a container 610 that has an outer wall 612 and a bottom 614. The film precursor evaporation system 600 also has a lid 620 hermetically bonded to the container 610, and the lid 620 is an outlet configured to be hermetically connected to a thin film deposition system as shown in FIG. 680. The container 610 and the lid 620 form a sealed environment when connected to the thin film deposition system. The container 610 and lid 620 are made of, for example, A6061 aluminum, which may or may not be coated.

  The container 610 is also coupled to a heater (not shown) to increase the evaporation temperature of the film precursor evaporation system 600, and temperature control is performed to perform at least one of monitoring, adjustment or control of the evaporation temperature. Configured to be coupled to a system (not shown). When the evaporation temperature reaches the above-mentioned proper value, the film precursor evaporates (or sublimates) to form a film precursor gas phase, which passes through the gas phase supply system, and the thin film deposition system. To be transported to. The container 610 is hermetically joined to the carrier gas supply system 4 (not shown), and the container 610 is configured to receive a carrier gas that conveys the film precursor gas phase.

  Referring again to FIG. 9, the film precursor evaporation system 600 further includes one or more stackable trays 640 that support the film precursor 650 and another stackable tray 640. It is configured to be installed or stacked on top. Each stackable tray 640 has a tray outer wall 642 and a tray inner wall 644 between which a film precursor 650 is held. The tray inner wall 644 defines a carrier gas supply space such as the central flux groove 618, and the carrier gas passes through this space through the tray inner wall 644 and flows to the upper part of the film precursor 650. The tray inner wall 644 further has a tray support end 643 that supports an additional tray 640. Accordingly, the second stackable tray 640 is installed to be supported by the lower tray support end 643 of the first stackable tray 640 and, if necessary, the subsequent stackable tray 640. One or more additional stackable trays are installed to be supported by the support end 643. The tray inner wall 644 of each stackable tray 640 has one or more tray openings 646 that are perimeters such as an annular space 660 of the container 610 from a carrier gas supply system (not shown). The carrier gas is configured to flow over the film precursor 650 through the central flux groove 618 toward the gas phase exhaust space forming the groove, and the carrier gas is formed in the lid 620 together with the film precursor gas phase. Exhaust through outlet 680. Therefore, the tray outlet wall 642 needs to be shorter than the tray inner wall 644 so that the carrier gas flows substantially radially into the annular space 660. Further, the level of the film precursor in each stackable tray 640 needs to be equal to or lower than the height of the tray outer wall 642 and below the position of the tray opening 646.

  The stackable tray 640 is drawn in a cylindrical shape. However, this shape may be changed. For example, the shape of the tray may be rectangular, square or oval. Similarly, the inner wall 644 and even the central flux wall 618 may have different shapes.

  When one or more stackable trays 640 are stacked on top of each other, a stack 670 is formed, and this stack is annular between the tray outer wall 642 of one or two stackable trays 640 and the container outer wall 612. A space 660 is provided. Container 610 further includes one or more spacers (not shown) configured to separate the outer tray wall 642 of one or more stackable trays 640 from the outer container wall 612. Thus, an equivalent space can be secured in the annular space 660. In an alternative embodiment, the container 610 is configured such that the tray outer wall 642 is vertically aligned. Container 610 may also include one or more thermal contact members (not shown) that provide mechanical contact between the inner wall of container 610 and the outer wall of each tray. Thus, heat energy can be transferred from the wall of the container 610 to each tray.

  A sealing device such as an O-ring may be installed between each tray and adjacent trays, in which case a vacuum seal is obtained between one tray and the next. For example, the sealing device may be placed in a receiving groove (not shown) formed in the tray support end 643 of the inner wall 642. In this case, once the tray is introduced into the container 310, the sealing of each sealing device is facilitated by joining the lid 620 and the container 610. The sealing device may have an elastomer O-ring, for example. Further, the sealing device may include, for example, a VITON (registered trademark) O-ring.

  The number of trays ranges from 2 to 20, for example, in one embodiment, the number of trays is 5, as shown in FIG. In one embodiment, the stack 670 has at least two stackable trays 640. The stack 670 may have a plurality of stack trays having a plurality of separable and stackable trays, or may have a single integrated piece with a plurality of trays integrated with each other. . The term integrated refers to a monolithic structure that does not have a clear boundary between trays, such as a monolithic structure, and a mechanically bonded structure with permanently bonded structures or trays installed It is necessary to understand that it includes a modified structure. The term separable should be understood to include those that do not have a junction or temporary junction between the trays, whether tight or mechanical.

Whether stackable or integral, the stackable tray 640 is configured to support the film precursor 650. In some embodiments, the film precursor 650 includes a solid precursor. In another example, the film precursor 650 has a liquid precursor. In another example, the film precursor 650 includes a metal precursor. In another example, the film precursor 650 includes a solid metal precursor. In yet another example, the film precursor 650 includes a carbonyl metal precursor. In yet another example, the film precursor 650 comprises a carbonyl ruthenium precursor, such as Ru ₃ (CO) ₁₂ . In yet another example, the film precursor 650 comprises a carbonyl rhenium precursor, such as Re ₂ (CO) ₁₀ . In yet another embodiment, the film precursor 650 is composed of W (CO) ₆ , Mo (CO) ₆ , Co ₂ (CO) ₈ , Rh ₄ (CO) ₁₂ , Cr (CO) ₆ or Os (CO) _12. including. In yet another embodiment, when tantalum (Ta) is deposited, the film precursor 650 is TaF ₅ , TaCl ₅ , TaBr ₅ , TaI ₅ , Ta (CO) ₅ , Ta [N (C _2). H ₅ CH ₃ )] ₅ (PEMAT), Ta [N (CH ₃ ) ₂ ] ₅ (PDMAT), Ta [N (C ₂ H ₅ ) ₂ ] ₅ (PDEAT), Ta (NC (CH ₃ ) ₃ ) (N (C ₂ H ₅ ) ₂ ) ₃ (TBTDET), Ta (NC ₂ H ₅ ) (N (C ₂ H ₅ ) ₂ ) ₃ , Ta (NC (CH ₃ ) ₂ C ₂ H ₅ ) (N ( CH ₃ ) ₂ ) ₃ , Ta (NC (CH ₃ ) ₃ ) (N (CH ₃ ) ₂ ) ₃ or Ta (EtCp) ₂ (CO) H. In yet another embodiment, when titanium (Ti) is deposited, the film precursor 650 is TiF ₄ , TiCl ₄ , TiBr ₄ , TiI ₄ , Ti [N (C ₂ H ₅ CH ₃ )]. ₄ (TEMAT), Ti [N (CH ₃ ) ₂ ] ₄ (TDMAT), Ti [N (C ₂ H ₅ ) ₂ ] ₄ (TDEAT) may be included. In still another embodiment, when ruthenium (Ru) is formed, the film precursor 650 includes Ru (C ₅ H ₅ ) ₂ , Ru (C ₂ H ₅ C ₅ H ₄ ) ₂ , Ru ( C ₃ H ₇ C ₅ H ₄ ) ₂ , Ru (CH ₃ C ₅ H ₄ ) ₂ , Ru ₃ (CO) ₁₂ , C ₅ H ₄ Ru (CO) ₃ , RuCl ₃ , Ru (C ₁₁ H ₁₉ O ₂ ) ₃ , Ru (C ₈ H ₁₃ O ₂ ) ₃ or Ru (C ₅ H ₇ O) ₃ .

  As described above, the film precursor 650 may include a solid precursor. The solid precursor may be in the form of a solid powder, or may be in the form of one or more solid tablets. For example, one or more solid tablets are prepared in a number of processing processes, including a sintering process, a stamping process, a dipping process, a spin coating process, or any combination thereof. The solid tablet-like solid precursor may or may not adhere to the stackable tray 640. For example, the refractory metal powder may be sintered at a temperature of 2000 ° C. to 2500 ° C. in a sintering furnace for vacuum and inert gas atmosphere. Alternatively, for example, the refractory metal powder may be dispersed in a fluid medium, distributed to the tray, and uniformly distributed on the tray surface using a spin coating process. The refractory metal spin coat is then thermally cured.

  As described above, the carrier gas may be supplied to the container 610 from a carrier gas supply system (not shown). As shown in FIG. 9, the carrier gas is supplied to the container 610 through the lid 620 via a gas supply line (not shown) hermetically joined to the lid 620. The gas supply line is connected to the central flux groove 618.

  Referring to FIG. 9 again, the inner diameter of the container outer wall 612 is, for example, in the range of about 10 m to about 100 cm, for example, in the range of about 15 cm to about 40 cm. For example, the inner diameter of the outer wall 612 may be 20 cm. The inner diameter of the outlet 622 and inner wall 644 of the stackable tray 640 is, for example, in the range of about 1 cm to about 30 cm, for example, the outlet diameter and inner wall diameter is in the range of about 5 to about 20 cm. For example, the outer diameter is 10 cm. Also, the outer diameter of each stackable tray 640 is from about 75% to about 99% of the inner diameter of the outer wall 612 of the container 610, for example, the tray diameter is from about 85% of the inner diameter of the outer wall 612 of the container 610. The range is 99%. For example, the diameter of the tray may be 19.75 cm. Also, the height of the tray inner wall 644 of each stackable tray 640 may range from about 5 mm to about 50 mm, for example, each height is about 30 mm. Also, the height of each outer wall 642 may range from about 10% to about 90% of the height of the inner wall 644 of the tray. For example, the height of each outer wall ranges from about 2 mm to about 45 mm, for example, from about 10 mm to about 20 mm. For example, the height of each inner wall is about 12 mm.

  Referring again to FIG. 9, one or more tray openings 646 may have one or more grooves. Alternatively, the one or more tray openings 646 may include one or more orifices. The diameter of each orifice is, for example, in the range of about 0.4 mm to about 2 mm. For example, the diameter of each orifice may be about 1 mm. In one embodiment, the diameter of the orifice and the diameter of the central flux groove 618 are selected such that the conductivity of the central flux groove 618 is sufficiently greater than the net conductivity of the orifice, and the central flux groove 618. The overall carrier gas distribution is maintained substantially uniform. The number of orifices is, for example, in the range of about 2 to about 1000, and in another embodiment in the range of about 50 to about 100. For example, one or more tray openings 646 may have 72 orifices with a diameter of 1 mm and the central flux groove 618 is approximately 10 to 30 mm.

  Further, the gas phase exhaust space, that is, the annular space 660 is designed to have high flux conductivity. For example, the net flux conductivity from the outlet of one or two tray openings in each tray to the outlet 680 of the container 610 is greater than about 50 liters / second, or the flux conductivity is about 100 liters / second. More than a second, or the flux conductivity is more than about 500 liters / second.

  Any of the film precursor systems 300, 300 ', 400, 500 or 600 may be used as the film precursor evaporation system 50 of FIG. 1 or the film precursor evaporation system 150 of FIG. Alternatively, the system 300, 300 ', 400, 500 or 600 may be used in any deposition system suitable for depositing a thin film from a precursor gas phase onto a substrate. For example, the deposition system includes a thermal chemical vapor deposition (CVD) system, a plasma accelerated CVD (PECVD) system, an atomic layer deposition (ALD) system, or a plasma accelerated ALD (PEALD) system.

  Referring to FIG. 10, this figure shows a method for forming a thin film on a substrate. A step of installing a thin film in the film forming system of the present invention will be described using a flowchart 700. In step 710, the substrate is placed in the film forming system, and the film formation is started, and the thin film is continuously formed on the substrate. For example, the film forming system may include any film forming system shown in FIGS. 1 and 2 described above. The film forming system includes a process chamber in which a film forming process is performed, and a substrate holder coupled to the process chamber and configured to support a substrate. Next, in step 720, a film precursor is introduced into the film forming system. For example, the film precursor is introduced into a film precursor evaporation system coupled to the process chamber via a precursor vapor supply system. Also, for example, the precursor vapor supply system may be heated.

  In step 730, the film precursor is heated to form a film precursor gas phase. The film precursor vapor phase is then transferred to the process chamber via the precursor vapor supply system. In step 740, the substrate is heated to a substrate temperature at which the film precursor gas phase is sufficiently decomposed, and in step 750, the substrate is exposed to the film precursor gas phase. Steps 710 to 750 may be repeated continuously a desired number of times, thereby depositing a metal film on the desired number of substrates.

  In step 760, after depositing a thin film on one or more substrates, a stack of trays 370, 370 ', 670, or one or more base or upper trays 330, 340, or one or more stacks. Possible trays 640 are periodically replaced and the amount of film precursor 350, 650 in each tray is replenished.

  Although only certain embodiments of the present invention have been described in detail, those skilled in the art will recognize that many variations can be made in certain embodiments without substantially departing from the innovative spirit and advantages of the present invention. Easy to understand. Accordingly, all such modifications are within the scope of the present invention.

It is a figure which shows the schematic of the film-forming system by the Example of this invention. It is a figure which shows the schematic of the film-forming system by another Example of this invention. 1 is a cross-sectional view of a film precursor evaporation system according to an embodiment of the present invention. FIG. 6 is a perspective view of a film precursor evaporation system according to another embodiment of the present invention. 2 is a cross-sectional view of a stackable upper tray used in a film precursor evaporation system according to an embodiment of the present invention. FIG. FIG. 5B is a perspective view of the tray of FIG. 5A. 2 is a cross-sectional view of a bottom tray used in a film precursor evaporation system according to an embodiment of the present invention. FIG. FIG. 6 is a cross-sectional view of a film precursor evaporation system according to another embodiment of the present invention. FIG. 6 is a cross-sectional view of a film precursor evaporation system according to another embodiment of the present invention. FIG. 6 is a cross-sectional view of a film precursor evaporation system according to another embodiment of the present invention. FIG. 2 illustrates a method for operating a film precursor evaporation system.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 Deposition system 1, 10 Process chamber, 20 Substrate holder, 25 Substrate, 38 Pump system, 40 Vapor phase precursor supply system, 50 Film precursor evaporation system, 110 Process chamber, 111 Upper chamber section, 120 Substrate holder, 121 Chamber temperature control system, 125 substrate, 130 gas phase dispersion system, 131 gas phase dispersion plate, 132 gas phase dispersion plenum, 133 processing zone, 134 orifice, 135 opening, 136 temperature control element, 140 gas phase precursor supply system, 150 Membrane precursor evaporation system, 154 precursor heater, 156 evaporation temperature control system, 300 membrane precursor evaporation system, 310 container, 314 bottom, 318 central groove, 320 lid, 322 outlet, 330 base tray, 332 base outer wall, 334 base Tray tray opening, 340 upper tray, 342 upper outer wall, 344 inner wall, 342 upper outer wall, 350 film precursor.

Claims (12)

A replaceable membrane precursor support assembly for use in a membrane precursor evaporation system having a container having an outer container wall and bottom and a lid configured to sealingly couple to the container,
The lid has an outlet configured to hermetically couple to a processing chamber configured to deposit a thin film on the substrate;
The replaceable membrane precursor support assembly is:
In the membrane precursor evaporation system, comprising a replaceable tray configured to support the membrane precursor and be laminated with one or more additional stackable trays;
The replaceable tray extends upward from the inner end to support a bottom support surface defined between an inner end and an outer end and the one or more additional stackable trays. And a stackable inner wall terminating at the upper support end, and an outer wall shorter than the stackable inner wall and extending upward from the outer end of the bottom support surface,
The film precursor is between the stackable inner wall and the outer wall on the bottom support surface;
The stackable inner wall forms a central flow channel in the container and the outer wall, the bottom support surface and the stackable inner wall form a tray space;
The replaceable tray has one or more tray openings on the stackable inner wall,
The one or more tray openings are configured such that carrier gas from a carrier gas supply system flows from the central flow channel through the one or more tray openings;
A carrier gas is discharged from the stackable inner wall together with the film precursor vapor from above the film precursor and the outer wall and through the outlet of the lid. Body support assembly. further,
The exchangeable membrane precursor of claim 1, comprising a membrane precursor supported between the stackable inner wall and the outer wall on the bottom support surface in the exchangeable tray. Support assembly.   The exchangeable membrane precursor support assembly according to claim 2, wherein the membrane precursor is a solid metal precursor supported on the exchangeable tray.   The exchangeable membrane precursor support assembly according to claim 3, wherein the membrane precursor is in the form of a solid powder or a solid tablet.   5. The exchangeable membrane precursor support assembly according to claim 3 or 4, wherein the membrane precursor is a carbonyl metal precursor supported on the exchangeable tray. The carbonyl metal precursor includes W (CO) ₆ , Mo (CO) ₆ , Co ₂ (CO) ₈ , Rh ₄ (CO) ₁₂ , Re ₂ (CO) ₁₀ , Cr (CO) ₆ , Ru ₃ (CO 6. The replaceable membrane precursor support assembly of claim 5 comprising ₁₂ or Os (CO) ₁₂ . The film _{precursor, TaF 5, TaCl 5, TaBr} 5, TaI 5, Ta (CO) 5, Ta [N (C 2 H 5 CH 3)] 5 (PEMAT), Ta [N (CH 3) 2] ₅ (PDMAT), Ta [N (C ₂ H ₅ ) ₂ ] ₅ (PDEAT), Ta (NC (CH ₃ ) ₃ ) (N (C ₂ H ₅ ) ₂ ) ₃ (TBTDET), Ta (NC ₂ H ₅ ) (N (C ₂ H ₅ ) ₂ ) ₃ , Ta (NC (CH ₃ ) ₂ C ₂ H ₅ ) (N (CH ₃ ) ₂ ) ₃ , Ta (NC (CH ₃ ) ₃ ) (N (CH ₃ ) ₂ ) ₃ , Ta (EtCp) ₂ (CO) H, TiF ₄ , TiCl ₄ , TiBr ₄ , TiI ₄ , Ti [N (C ₂ H ₅ CH ₃ )] ₄ (TEMAT), Ti [N (CH _{3) 2] 4 (TDMAT)} , Ti [N (C 2 H 5) 2 _{4 (TDEAT), Ru (C} 5 H 5) 2, Ru (C 2 H 5 C 5 H 4) 2, Ru (C 3 H 7 C 5 H 4) 2, Ru (CH 3 C 5 H 4) 2 , Ru ₃ (CO) ₁₂ , C ₅ H ₄ Ru (CO) ₃ , RuCl ₃ , Ru (C ₁₁ H ₁₉ O ₂ ) ₃ , Ru (C ₈ H ₁₃ O ₂ ) ₃ or Ru (C ₅ H ₇ O ) includes one or more of the _three or replaceable film precursor support assembly of claim 3 or 4, characterized in that it comprises a combination of two or more thereof. A film precursor evaporation system configured to be coupled to a thin film deposition system comprising:
A container having an outer container wall, a container bottom, and a removable container lid hermetically coupled to the outer container wall, the lid being hermetically coupled to an inlet of the thin film deposition system;
A plurality of replaceable trays according to claim 1 stacked in said container;
A film precursor evaporation system. A thin film deposition system for forming a thin film on a substrate,
A film precursor evaporation system according to claim 8,
further,
A processing chamber having a substrate holder configured to support and heat the substrate;
A vapor distribution system configured to introduce a film precursor vapor above the substrate;
An exhaust system configured to depressurize the processing chamber;
Have
The outlet of the container is connected to the vapor distribution system. A film precursor evaporation system configured to be coupled to a thin film deposition system comprising:
A container having an outer container wall and a bottom and coupled to a heater and configured to be heated;
A lid configured to be hermetically coupled to the container, the lid having an outlet configured to be hermetically coupled to the thin film deposition system;
A stack of trays,
A said bottom base tray which is supported on part of the vessel, 1 or an inner wall stackable having a base support edge for supporting two or more additional stackable trays, than the stackable inner wall A base tray having a short outer wall, the outer wall and the stackable inner wall configured to hold a film precursor therebetween.
In one or more upper trays including a first upper tray supported on the base support end and one or more optional additional upper trays supported on the first upper tray There,
The first upper tray has an upper stackable inner wall having an upper support end that supports the one or more optional additional upper trays ;
Each of the one or more optional additional upper trays is configured to be positioned over any preceding optional additional upper tray, the upper supporting one or more optional additional upper trays Having an upper laminateable inner wall with a support end;
Each of the first upper tray and one or more optional additional upper trays has an upper outer wall that is shorter than the upper stackable inner wall;
The upper outer wall and the upper stackable inner wall of each of the one or more upper trays are configured to hold the film precursor therebetween, the stackable inner wall of the base tray; and The upper stackable inner walls of the one or more upper trays form one or more upper trays forming a central flow channel in the container;
A stack of trays having;
An annular space between the outer wall and the outer container wall of the stack of trays, the annular space configured to couple with the thin film deposition system;
One or more openings disposed in the stackable inner wall of the base tray and coupled to the central flow channel, wherein a first portion of carrier gas is removed from the central flow channel and the base tray is Through the upper portion of the film precursor of the base tray, and flow toward the annular space, and together with the film precursor vapor, the carrier gas is exhausted through the outlet of the lid, One or more openings;
1 or 2 disposed on the upper stackable inner wall of the first upper tray and the upper stackable inner wall of each of the one or more optional additional upper trays and coupled to the central flow channel Two or more top openings;
Have
The one or more top openings in the first top tray allow a second portion of carrier gas to pass from the central flow channel through the first top tray and into the first top tray. The carrier gas passes above the film precursor and above the outer wall of the first upper tray, flows toward the annular space, and exhausts the carrier gas together with the film precursor vapor through the outlet of the lid. Configured to
The base tray and the first upper tray are:
The first portion of the carrier gas does not flow via the one or more upper trays, and the second portion of the carrier gas does not flow via the base tray, or the one or more A film precursor evaporation system configured to prevent flow through any additional top tray. A thin film deposition system comprising the film precursor evaporation system according to claim 10,
further,
A heater coupled to the container and configured to heat and heat the container;
A deposition chamber having an inlet coupled to the outlet of the container;
A thin film deposition system. A film forming system for forming a thin film on a substrate, comprising the film precursor evaporation system according to claim 10,
further,
A processing chamber, a substrate holder configured to support the substrate and to heat the substrate; a vapor distribution system configured to introduce film precursor vapor on top of the substrate; and the processing A processing chamber having an exhaust system configured to depressurize the chamber;
A steam supply system having a first end hermetically coupled to the outlet of the vessel and a second end hermetically coupled to an inlet of the steam distribution system of the processing chamber;
A film forming system.

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