EP4122006A1 - Procédé de traitement de substrats avec produits chimiques - Google Patents

Procédé de traitement de substrats avec produits chimiques

Info

Publication number
EP4122006A1
EP4122006A1 EP21707631.4A EP21707631A EP4122006A1 EP 4122006 A1 EP4122006 A1 EP 4122006A1 EP 21707631 A EP21707631 A EP 21707631A EP 4122006 A1 EP4122006 A1 EP 4122006A1
Authority
EP
European Patent Office
Prior art keywords
treatment medium
substrate
treatment
temperature
chemical
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP21707631.4A
Other languages
German (de)
English (en)
Inventor
Harald Okorn-Schmidt
Manuel LINDER
Jörg HOFER-MOSER
Philipp Tobias ENGESSER
Klaus Smoliner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
4tex GmbH
Original Assignee
4tex GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 4tex GmbH filed Critical 4tex GmbH
Publication of EP4122006A1 publication Critical patent/EP4122006A1/fr
Pending legal-status Critical Current

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P50/00—Etching of wafers, substrates or parts of devices
    • H10P50/60—Wet etching
    • H10P50/66—Wet etching of conductive or resistive materials
    • H10P50/663—Wet etching of conductive or resistive materials by chemical means only
    • H10P50/667—Wet etching of conductive or resistive materials by chemical means only by liquid etching only
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
    • H10P72/04—Apparatus for manufacture or treatment
    • H10P72/0402—Apparatus for fluid treatment
    • H10P72/0404—Apparatus for fluid treatment for general liquid treatment, e.g. etching followed by cleaning
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04K—SECRET COMMUNICATION; JAMMING OF COMMUNICATION
    • H04K1/00—Secret communication
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04L—TRANSMISSION OF DIGITAL INFORMATION, e.g. TELEGRAPHIC COMMUNICATION
    • H04L63/00—Network architectures or network communication protocols for network security
    • H04L63/18—Network architectures or network communication protocols for network security using different networks or channels, e.g. using out of band channels
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P50/00—Etching of wafers, substrates or parts of devices
    • H10P50/20—Dry etching; Plasma etching; Reactive-ion etching
    • H10P50/28—Dry etching; Plasma etching; Reactive-ion etching of insulating materials
    • H10P50/282—Dry etching; Plasma etching; Reactive-ion etching of insulating materials of inorganic materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
    • H10P72/04—Apparatus for manufacture or treatment
    • H10P72/0402—Apparatus for fluid treatment
    • H10P72/0418—Apparatus for fluid treatment for etching
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
    • H10P72/04—Apparatus for manufacture or treatment
    • H10P72/0402—Apparatus for fluid treatment
    • H10P72/0418—Apparatus for fluid treatment for etching
    • H10P72/0422—Apparatus for fluid treatment for etching for wet etching
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
    • H10P72/04—Apparatus for manufacture or treatment
    • H10P72/0402—Apparatus for fluid treatment
    • H10P72/0418—Apparatus for fluid treatment for etching
    • H10P72/0422—Apparatus for fluid treatment for etching for wet etching
    • H10P72/0426—Apparatus for fluid treatment for etching for wet etching with the semiconductor substrates being dipped in baths or vessels
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
    • H10P72/04—Apparatus for manufacture or treatment
    • H10P72/0448—Apparatus for applying a liquid, a resin, an ink or the like
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04K—SECRET COMMUNICATION; JAMMING OF COMMUNICATION
    • H04K1/00—Secret communication
    • H04K1/003—Secret communication by varying carrier frequency at or within predetermined or random intervals
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04K—SECRET COMMUNICATION; JAMMING OF COMMUNICATION
    • H04K1/00—Secret communication
    • H04K1/006—Secret communication by varying or inverting the phase, at periodic or random intervals
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04K—SECRET COMMUNICATION; JAMMING OF COMMUNICATION
    • H04K1/00—Secret communication
    • H04K1/08—Secret communication by varying the polarisation of transmitted waves
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04L—TRANSMISSION OF DIGITAL INFORMATION, e.g. TELEGRAPHIC COMMUNICATION
    • H04L1/00—Arrangements for detecting or preventing errors in the information received
    • H04L1/0001—Systems modifying transmission characteristics according to link quality, e.g. power backoff
    • H04L1/0023—Systems modifying transmission characteristics according to link quality, e.g. power backoff characterised by the signalling
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P50/00—Etching of wafers, substrates or parts of devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P50/00—Etching of wafers, substrates or parts of devices
    • H10P50/20—Dry etching; Plasma etching; Reactive-ion etching
    • H10P50/26—Dry etching; Plasma etching; Reactive-ion etching of conductive or resistive materials
    • H10P50/264—Dry etching; Plasma etching; Reactive-ion etching of conductive or resistive materials by chemical means
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P50/00—Etching of wafers, substrates or parts of devices
    • H10P50/20—Dry etching; Plasma etching; Reactive-ion etching
    • H10P50/28—Dry etching; Plasma etching; Reactive-ion etching of insulating materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P50/00—Etching of wafers, substrates or parts of devices
    • H10P50/60—Wet etching
    • H10P50/64—Wet etching of semiconductor materials
    • H10P50/642—Chemical etching
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P50/00—Etching of wafers, substrates or parts of devices
    • H10P50/73—Etching of wafers, substrates or parts of devices using masks for insulating materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
    • H10P72/06—Apparatus for monitoring, sorting, marking, testing or measuring
    • H10P72/0602—Temperature monitoring
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
    • H10P72/06—Apparatus for monitoring, sorting, marking, testing or measuring
    • H10P72/0604—Process monitoring, e.g. flow or thickness monitoring
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P90/00—Preparation of wafers not covered by a single main group of this subclass, e.g. wafer reinforcement
    • H10P90/12—Preparing bulk and homogeneous wafers
    • H10P90/126—Preparing bulk and homogeneous wafers by chemical etching

Definitions

  • the invention relates to a method for treating substrates with chemicals.
  • treatment media When processing substrate surfaces, such as silicon or other semiconductor materials, complex and expensive mixtures of chemicals (“treatment media”) are often used.
  • the aim of processing substrate surfaces is, among other things, to selectively remove layers of the substrate that are no longer required from underlying layers of the substrate.
  • etching mixtures as the treatment medium, contain water or an organic solvent as the main component, which in certain cases also serves as an inert matrix, and other active components, for example an inorganic or organic acid or an inorganic or organic base.
  • the mixtures of chemicals used for treating substrate surfaces contain, for example, treatment media that are used in the manufacture of integrated circuits, and other components.
  • additional components can be buffer substances in order to stabilize the pH value, since the acid concentration or the base concentration can change during the etching process.
  • Corrosion inhibitors are often added to mixtures of treatment media containing chemicals, which are intended to ensure that certain materials which are exposed to the treatment medium, for example the etching mixture, are not attacked (not etched).
  • oxidizing agents are also added to the etching mixtures, which are necessary are, for example, to convert metals into their ionized, soluble chemical states.
  • etch mixtures used in the manufacture of semiconductors contain several components in certain concentrations in order to be effective.
  • the concentrations of the chemicals that are particularly suitable for carrying out the substrate treatment, in particular for etching are obtained, for example, from experiments in which the etching rates of the exposed materials are measured and their etching selectivities are determined therefrom. It is often desirable to obtain high etching rates, as this enables the process times to be kept short.
  • water also has the task of causing the dissociation (activation) of the acid or base and thus serves to finally dissolve the etching residues and the materials which are soluble in the etching medium and formed during the etching.
  • a problem that arises in particular when etching substrate surfaces is that the process time can be very long, since the etching cannot always be optimized by increasing the concentration and / or increasing the temperature.
  • a specific method in which this problem occurs is the removal of a coating, for example a structured or unstructured masking layer ("hard mask, HM)," during the process sequence to prepare for the creation of electrical contacting and wiring of the electronic components applied to microchips
  • a coating for example a structured or unstructured masking layer ("hard mask, HM)," during the process sequence to prepare for the creation of electrical contacting and wiring of the electronic components applied to microchips
  • the area of microchip and component production is generally referred to as the "back end of line” (BEOL), the process area for creating the Metal contacts, designated.
  • a typical masking layer can, for example, be a coating made of titanium nitride (TiN).
  • hydrogen peroxide When etching this masking layer, hydrogen peroxide is used, for example, which decomposes to oxygen and water in the basic pH range and at higher temperatures and possibly also through prolonged contact with titanium ions and is then no longer available in a sufficiently high concentration as an oxidizing agent for titanium nitride.
  • the oxidation of titanium nitride is necessary, however, so that the material of the masking layer can be dissolved in the etching medium.
  • Hydrogen peroxide can also decompose in the neutral and acidic pH range. Etching mixtures for relevant materials in these pH ranges can be advantageous if special etching selectivities between two specific materials are necessary.
  • Masking layers are also used in other areas of the manufacture of semiconductor components, such as in FEOL ("front end of line”, process area for creating critical electronic components, for example transistors), MoL ("middle of line", process area for creating the first critical electrical contacts to the critical components).
  • FEOL front end of line
  • MoL middle of line
  • process area for creating the first critical electrical contacts to the critical components An example of a further process area where masking layers are used is the so-called “back end” (BE, area of the final process steps for the separation and packaging of the microchips or components).
  • mixtures of chemicals treatment media
  • the mixture of chemicals e.g. 40 liters
  • the specified process temperature e.g. 60 °
  • the invention is based on the object of specifying a method of the type mentioned at the outset which, while being highly effective, results in a lower consumption of chemicals. This object is achieved according to the invention with a method which has the features of claim 1.
  • the treatment medium used to treat the substrate which contains at least one chemical effective for the treatment, is heated to a temperature in a predetermined temperature range at which the chemical is still sufficiently stable.
  • the treatment medium is heated in a very short time to the temperature required for the process (process temperature) immediately before being applied to the substrate, so that no or only slight and negligible decomposition of the at least one chemical occurs in the short time.
  • the procedure can be such that the treatment medium is heated to a temperature immediately before application to the substrate, so that it has the optimum temperature for the effective processing of the substrate at the time when the treatment medium occurs on the substrate, and so on good result of processing (process result) is achieved.
  • the method according to the invention is suitable for processing substrates with non-recyclable (reusable) treatment media, such as, for example, those containing hydrogen peroxide, which is used for removing titanium nitride layers during wafer production.
  • non-recyclable (reusable) treatment media such as, for example, those containing hydrogen peroxide, which is used for removing titanium nitride layers during wafer production.
  • An advantageous effect of the method according to the invention is that because of the short-term increase in temperature to an optimal temperature for effective processing of the substrate, this temperature increase occurring immediately before the treatment medium is applied to the substrate, there is only a very short period of time within which the active chemical (e.g. hydrogen peroxide) cannot or only slightly decomposes.
  • Another advantage of the method according to the invention is that large areas of the apparatus and devices used for carrying out the method according to the invention do not have to be designed in such a way that they have to withstand high temperatures, since they are only exposed to low temperatures.
  • the following devices can be used to heat the treatment medium:
  • Resistance heater using a heating element The heating element is connected to a direct voltage or alternating voltage, in particular high-frequency alternating voltage, by means of two electrical contacts. Due to the specific resistance of the material, a certain current can flow, which generates heat and heats the material. The material is in direct or indirect contact, separated by a separating material or a coating, with the medium to be heated. The medium washes around the heating element and dissipates the heat. A material for direct contact with the medium could be glassy carbon, for example.
  • Resistance heater using a heating medium Electrical heating via contact electrodes that are in direct electrical contact with the heating medium. The heating medium is heated by means of direct current or low or high frequency alternating current because of its specific resistance.
  • the advantage of this method lies in the fact that there is no thermal mass of the heating element.
  • the design is galvanically separated in order to avoid voltage potentials through the medium.
  • the contact electrodes can be made of glassy carbon, for example.
  • the geometry and positioning of the contacts should be selected in a way that is advantageous for the heating of the medium.
  • Heat exchanger • Heating by blowing in steam. Introduction of pure water vapor or superheated water vapor into the medium.
  • Temperature control by mixing media with different temperatures For example, a cold medium is combined with a warm medium via separate lines and separately controllable control valves in a mixed line.
  • the mixed temperature can be set through the different and individually controllable inflow of cold and warm medium (cf. AT 515 147 Bl).
  • the invention solves the problem by dividing the heating of the treatment medium into two steps:
  • the treatment medium is heated according to the point of impact on the substrate (wafer) in order to achieve an optimal process result.
  • the invention can be used for many processes in the semiconductor and component manufacturing process (such as in FEOL, BEOL, MOL and BE); also for the removal of unwanted contamination, e.g. when cleaning substrates.
  • the main application is in the area of non-recirculable treatment media, and here especially in the area of media that contain H2O2 (or other time or temperature-dependent unstable oxidizing agents), and there in particular in processes for removing masking layers made of TiN (or other selectively removable, and for masking suitable materials).
  • FIG. 1 shows, in section, a typical microstructure arrangement on a semiconductor substrate, which schematically shows the process area for creating the metal contacts (only the details relevant to understanding the present invention are shown, parts of the material layers required for a functioning electronic circuit are not shown),
  • FIG. 2 shows a diagram of etching rate / temperature
  • FIG. 3 shows a diagram of etching rate / distance to the center
  • FIG. 4 shows a diagram of etching rate / diameter
  • FIG. 5 shows a diagram of etching rate / diameter.
  • a semiconductor substrate 110 shown in FIG. 1 has a masking layer (for example TiN hard mask) 101 on its front side.
  • An opening 102 was made in the masking layer 101 via a series of lithography-relevant processes, so that a trench 103 could be etched in the dielectric 109 with the dielectric constant kl (kl usually has a value in the BEOL range that is below the value k of thermal S1O2).
  • a cover layer 105 which is exposed after the dry etching processes.
  • a metal film 107 which is divided into an intermediate layer 108, a dielectric with the dielectric constant k2 (k2 in the BEOL range usually has a value that is below the value k of thermal S1O2; kl and k2 can also have the same k Have value, ie the layers 108 and 109 can consist of the same or very similar materials), is embedded.
  • the masking layer 101 is selectively removed without the exposed area of the cover layer 105 or the Interlayer 109 are chemically attacked or corroded.
  • the metal film 107 can also be exposed.
  • a treatment medium etching medium
  • the material layers to be removed can be located on the front side of the substrate or on the rear side thereof.
  • the material layers can be layers of many different elements and combinations of elements
  • Si Si, SiGe, Ge, SiC, Ti0 2 , III / V (GaAs, InGaAs, GaN and other materials with similar semiconductor properties).
  • Conductor PolySi (with or without doping), W, Co, Cu, Mo, Ti,
  • TiN, Ta, TaN, BN, Graphene can also act as a semiconductor under certain conditions) and Sn compounds.
  • Insulator Si oxide, Si nitride, Al oxide, low-k materials (materials with a low dielectric constant: k typically lower than the dielectric constant of thermally generated Si0 2) , high-k materials (materials with a high dielectric constant: k typically higher than the dielectric constant of thermally generated Si0 2 , eg Hf oxide).
  • Auxiliary films masking layers (hard masks), photo films, block masks, planarization layers, which can consist of many of the above-mentioned elements and element connections.
  • Treatment media used that have different removal rates depending on the temperature. In almost all cases the etching rate increases when the temperature of the treatment medium is increased.
  • treatment media When removing a TiN masking layer, treatment media are used that dissolve the TiN in two stages.
  • the first step is the oxidation of the Ti / TiN
  • the TiO x , Ti x O y , Ti x OH y , or T1O2 is dissolved.
  • H2O2 is used for the oxidation.
  • Other oxidizing agents are also possible, such as, for example, percarbonates, oxo anions, permanganates, dichromates, oxidizing metal ions (for example noble metal ions), anions of halogenated oxygen acids, or oxidizing elements such as oxygen, sulfur and halogens.
  • the oxides then often dissolve in the pH range above 7, mostly in a pH range between 7 and 10. Etching mixtures in the pH range 7 and below may also be desirable, for example in order to achieve a certain selectivity for the etching of two materials allow relative to each other.
  • Example of a possible process sequence a) applying the TiN masking layer, b) structuring the TiN masking layer / opening the masking layer, c) Dry etching of the material in the open area of the TiN masking layer, d) Removal of the TiN masking layer and the dry etching by-products:
  • the removal of the TiN masking layer and the dry etching by-products can be carried out in one step or in two successive steps.
  • a mixture of a base eg TMAH, NH 4 OH, TEAH
  • an oxidizing agent eg H 2 O 2
  • water is used as a typical treatment medium.
  • a mixture of a base eg TMAH (tetramethylammonium hydroxide), NH 4 OH, TEAH (tetraethylammonium hydroxide)
  • an oxidizing agent eg H 2 O 2
  • water is used as a typical treatment medium.
  • Diluted HF hydrofluoric acid
  • a typical treatment medium which can also contain chemical additives to prevent unwanted corrosion on existing materials, e.g. citric acid or benzotriazole.
  • the targeted control of atmospheric oxygen and light can also be advantageous in order to be able to control corrosion processes in a targeted manner.
  • the treatment medium within the system is heated to the temperature at which the chemical contained in the treatment medium is still stable. This temperature depends on the mixture and can be between 30 ° C and 70 ° C.
  • the treatment medium is now increased from the temperature to which the treatment medium was heated in the system to a temperature which results in an optimal process temperature on the substrate.
  • the temperature difference between the system and the end point of the line can be between 5 ° C and 80 ° C.
  • the higher temperature reduces the time that is required to remove the TiN masking layer. In addition, this reduces the amount of treatment media required.
  • the masking layer 101 is typically removed after the dry etching processes, which are used to define the trench 103 and the contact hole 104, have been completed.
  • the increased difficulty arises because of the materials (cover layer materials 105 or metal films 107) that can be exposed during dry etching, e.g. Cu, Co, CoWP, Ta,
  • TaN or Ru to name just a few of the materials currently in use. These materials, which are used to distribute the currents within the semiconductor chip, must be protected from oxidation and dissolution.
  • anti-corrosive agents are added to the treatment medium, which are often organic inhibitors that prevent unwanted attack on the metals through absorption or adsorption on the surface, e.g. BTA (benzotriazole) is used, or citric acid.
  • BTA benzotriazole
  • citric acid e.g. citric acid
  • FIG. 3 Diagrams of the etching profiles at 55 ° C. with central (in the center of rotation of the substrate) and decentralized (outside the center of rotation of the substrate) application of the etching medium (no additional heating of the treatment medium before application) are shown in FIG. 3.
  • FIG. 4 A diagram of the etching rates when the temperature is increased from 55 ° C. to 65 ° C. without temperature compensation, i.e. without adapting the heating temperature as a function of the radial distance of the application point from the rotation center of the substrate, during application is shown in FIG. 4.
  • FIG. 5 shows a diagram of the etching rate with a temperature increase from 55 ° C. to 65 ° C. and additional temperature compensation during application.
  • the temperature of the treatment medium is optimally adapted to the point of application on the wafer.
  • the temperature is increased from 65 ° C in the center to 67.5 ° C at a radial distance of 60 mm from the center.
  • the increase takes place linearly as a function of the position and in such a way that the optimum temperature was reached at the time of impact on the substrate.
  • the treatment medium is an aqueous solution which contains 5% by volume
  • H2O2 150ppm tetramethylammonium hydroxide and 200ppm 1,2,4-triazole.
  • the standard process results in an etching rate at 50 ° C (temperature on the substrate) of 216 A / min, which results in a process time of 83 seconds for a TiN layer of 300 A to be removed.
  • the treatment medium is an aqueous solution, which contains 10Vol% H2O2, 200ppm choline hydroxide and 150ppm 1,2,3-triazole.
  • the standard process results in an etching rate at 55 ° C (temperature on the substrate) of 226 A / min, which results in a process time of 93 seconds for a TiN layer of 350 A to be removed.
  • the process according to the invention with a targeted increase in the temperature immediately before application to the substrate, so that the contact temperature of the treatment medium on the substrate is increased by 10 ° C., results in an etching rate of 454 A / min, which is 350 A for a TiN layer to be removed results in a process time of 46 seconds.
  • the treatment medium is an aqueous solution which contains 15 vol% H2O2, 150ppm tetramethylammonium hydroxide and 550ppm imidazole.
  • the standard process results in an etching rate at 50 ° C (temperature on the substrate) of 196 A / min, which results in a process time of 76 seconds for a TiN layer of 250 A to be removed.
  • the process according to the invention with a targeted increase in the temperature immediately before application to the substrate, so that the contact temperature of the treatment medium on the substrate is increased by 15 ° C, results in an etching rate of 554 A / min, which results in a process time of 27 seconds for a TiN layer of 250 A to be removed.
  • the treatment medium is an aqueous solution which contains 20% by volume H2O2, 200 ppm choline hydroxide and 200 ppm imidazole.
  • the standard process results in an etching rate at 50 ° C (temperature on the substrate) of 226 A / min, which results in a process time of 92 seconds for a TiN layer of 350 A to be removed.
  • the treatment medium When treating substrates with a treatment medium which contains at least one chemical effective for the treatment, For example, when removing a masking layer 101 from a semiconductor substrate 110 by etching, the treatment medium is only heated to a temperature effective for the treatment immediately before being applied to the substrate 110, the treatment medium having the optimal temperature for the treatment when it is applied to the substrate meets. In this way, a short treatment time, low, thermally induced decomposition losses of chemicals and a saving in treatment medium are achieved.

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  • Engineering & Computer Science (AREA)
  • Computer Networks & Wireless Communication (AREA)
  • Signal Processing (AREA)
  • Computer Hardware Design (AREA)
  • Computer Security & Cryptography (AREA)
  • Computing Systems (AREA)
  • General Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Weting (AREA)
  • Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
  • Drying Of Semiconductors (AREA)

Abstract

Selon l'invention, lors du traitement de substrats avec un milieu de traitement contenant au moins un produit chimique efficace pour le traitement, par exemple lors du retrait d'une couche de masquage (101) à partir d'un substrat semi-conducteur (110) par gravure, le milieu de traitement est chauffé à une température efficace pour le traitement uniquement immédiatement avant l'application sur le substrat (110), le milieu de traitement étant à la température optimale pour le traitement lorsqu'il frappe le substrat. Ainsi, un temps de traitement court, des pertes de décomposition faibles, induites thermiquement de produits chimiques et une économie de milieu de traitement sont obtenus.
EP21707631.4A 2020-02-20 2021-02-17 Procédé de traitement de substrats avec produits chimiques Pending EP4122006A1 (fr)

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ATGM21/2020U AT16977U3 (de) 2020-02-20 2020-02-20 Verfahren zum Behandeln von Substraten mit Chemikalien
PCT/EP2021/053867 WO2021165308A1 (fr) 2020-02-20 2021-02-17 Procédé de traitement de substrats avec produits chimiques

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JP7636425B2 (ja) 2025-02-26
AT16977U3 (de) 2021-03-15
AT16977U2 (fr) 2021-01-15
WO2021165308A1 (fr) 2021-08-26
JP2023519493A (ja) 2023-05-11

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