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WO2017039624A1 - Procédé de formation d'une ouverture de trou d'interconnexion - Google Patents

Procédé de formation d'une ouverture de trou d'interconnexion Download PDF

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Publication number
WO2017039624A1
WO2017039624A1 PCT/US2015/047795 US2015047795W WO2017039624A1 WO 2017039624 A1 WO2017039624 A1 WO 2017039624A1 US 2015047795 W US2015047795 W US 2015047795W WO 2017039624 A1 WO2017039624 A1 WO 2017039624A1
Authority
WO
WIPO (PCT)
Prior art keywords
via opening
desmearing
agent
species
active
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.)
Ceased
Application number
PCT/US2015/047795
Other languages
English (en)
Inventor
Robert Alan May
Vikram SHISHODIA
Sri Ranga Sai Boyapati
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.)
Individual
Original Assignee
Individual
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 Individual filed Critical Individual
Priority to PCT/US2015/047795 priority Critical patent/WO2017039624A1/fr
Publication of WO2017039624A1 publication Critical patent/WO2017039624A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/0011—Working of insulating substrates or insulating layers
    • H05K3/0055—After-treatment, e.g. cleaning or desmearing of holes
    • H10W70/097—
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
    • H05K2203/0779—Treatments involving liquids, e.g. plating, rinsing characterised by the specific liquids involved
    • H05K2203/0786—Using an aqueous solution, e.g. for cleaning or during drilling of holes
    • H05K2203/0796—Oxidant in aqueous solution, e.g. permanganate
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/0011—Working of insulating substrates or insulating layers
    • H05K3/0017—Etching of the substrate by chemical or physical means
    • H05K3/0026—Etching of the substrate by chemical or physical means by laser ablation
    • H05K3/0032—Etching of the substrate by chemical or physical means by laser ablation of organic insulating material
    • H05K3/0035—Etching of the substrate by chemical or physical means by laser ablation of organic insulating material of blind holes, i.e. having a metal layer at the bottom
    • H10P70/234—
    • H10W70/095—
    • H10W70/635—

Definitions

  • the vias that form electrical interconnections between metal layers in an integrated circuit (IC) substrate are generally initially formed using a laser.
  • the vias that are formed by using a laser are typically tapered (i.e., wider at the top than the bottom). This tapering often results in a narrow via bottom that causes concerns relative to the reliability of the via and its ability to conduct electrical current.
  • Using a laser to form a tapered opening for a via also usually leaves behind organic residue in the opening.
  • the organic residue is commonly known as smear.
  • Smear is typically addressed through a chemistry based removal process known as desmear.
  • the conventional desmear process suffers from a variety of drawbacks.
  • conventional desmear roughens the outer surface of the dielectric. Since this outer surface is used as the base for the next Cu layer the dielectric roughness is translated to the next layer's Cu trace. This roughening of the conductive surface may negatively impact electrical performance of the IC that includes the via.
  • FIG. 1 is a flow diagram illustrating an example method of forming a via opening in an electric component.
  • FIG. 2 is a flow diagram illustrating another example method of forming a via opening in an electric component.
  • FIG. 3 is a flow diagram illustrating yet another example method of forming a via opening in an electric component.
  • FIG. 4 illustrates an example via opening in an electronic component before a desmearing agent has been inserted into the via opening.
  • FIG. 5 shows the via opening of FIG. 4 after a desmearing agent has been inserted in to the via opening.
  • FIG. 6 shows the via opening of FIG. 5 being rinsed with a solution to remove the desmearing agent and solubilized reaction products.
  • FIG. 7 shows the via opening after the rinsing operation of FIG.
  • FIG. 8 shows an example via opening before a desmearing agent that includes an active third species has been inserted into the via opening 10.
  • FIG. 9 shows the via opening of FIG. 8 after a desmearing agent that includes an active third species has been inserted in to the via opening to roughen the via opening.
  • FIG. 10 shows the via opening of FIG. 9 after removing the desmearing agent that includes an active third species from the via opening.
  • FIG. 11 is block diagram of an electronic apparatus that includes the methods described herein.
  • the methods described herein may utilize a geometry of a via in combination with fact that radicals decay approximately with distance squared to (i) widen the via bottom; and/or (iii) clean smear from the via.
  • the method may clean smear from an exposed conductor (e.g., copper) without roughening the outer surface of the conductor.
  • the method may be accomplished in a single solution that includes an inactive desmear agent, an initiator that forms radicals upon contact with Cu(0) and a deactivator.
  • an inactive desmear agent an initiator that forms radicals upon contact with Cu(0) and a deactivator.
  • One example method may be summarized as follows:
  • the initiator contacts the Cu(0) pad and generates radicals.
  • the radicals activate the desmear agent. In some forms, more radicals are activated near the Cu surface due to short lifetime of the radicals.
  • the desmear agent removes organic material until it meets the deactivator. Controlling the amount of deactivator within the solution may allow for some control over the final via shape. This control over the final via shape may be accomplished by balancing the ratio of radicals to deactivator.
  • FIG. 1 is a flow diagram illustrating an example method [100] of forming a via opening 10 in an electronic component 11.
  • FIG. 4 shows an example via opening 10 before the method [100] is applied to the via opening 10.
  • the method [100] includes [110] inserting a desmearing agent 12
  • the desmearing agent 12 includes a first species R which forms radicals R° when coming into contact with a conductor 14 within the via opening 10.
  • the radical R° activates an inactive second species to form an active second species 15 that is part of the desmearing agent 12.
  • the active second species 15 converts smear 13 within the via opening 10 to solubilized reaction products.
  • the method [100] further includes [120] rinsing the via opening
  • FIG. 6 shows the via opening 10 being rinsed with a solution 18 (e.g., an acidic solution such as sulfuric acid, hydrochloric acid or oxalic acid) to remove the desmearing agent 12 and the solubilized reaction products.
  • a solution 18 e.g., an acidic solution such as sulfuric acid, hydrochloric acid or oxalic acid
  • FIG. 7 shows the via opening of FIGS. 4-6 after the [120] rinsing operation.
  • inserting a desmearing agent 12 into a via opening 10 to remove smear 13 from the via opening 10 includes inserting the electrical component 11 into a chemical bath. It should be noted other forms of inserting the desmearing agent 12 into the via opening 10 are contemplated (e.g., spray, immersion or flood type).
  • the inactive second species may have an electrochemical potential such that the inactive second species does not oxidize the smear 13.
  • the active second species may have an electrochemical potential
  • the method [100] described herein may remove smear 13 from the bottom of the via opening 10 that has been drilled (e.g., laser drilled) while still permitting control of the via opening 10 shape and surface roughness.
  • An example radical activated desmearing process is shown in equations 2 through 5 and illustrated in FIG. 5.
  • Radicals are generated at the Cu surface and activate the desmearing agent 12. There may be more radical activation at the bottom of the via opening 10 than the top of the via opening 10 (see FIG. 5). This distribution of the radical activation in the via opening 10 may promote a wider bottom at the via opening 10 and some amount of Cu removal depending on the components used (see FIG. 7).
  • the conductor 14 may be copper and that some copper may be etched. This copper etching may actually be desirable for via integrity because an undercut 16 may be created. Creating an undercut 16 may be especially useful for fine pitch via openings 10 because the undercut serves as anchor to provide the fine pitch via with additional strength.
  • the method [100] may allow for some control over the surface morphology of the dielectric layer 17.
  • adhesion which favors high surface roughness of the dielectric material
  • electrical performance which favors low surface roughness on the conductor 14.
  • an active oxidizer may be added to the desmearing agent 12 in order permit some control of the surface morphologies for the dielectric layer 17 and the conductor 14.
  • the desmearing agent 12 includes a deactivator that makes some of the radicals in the first species inactive in order to control a width of the via opening 10.
  • adding more deactivator into the desmearing agent 12 may reduce the effect of the radicals on the via opening 10, and adding less deactivator into the desmearing agent 12 may increase the effect of the radicals on the via opening 10.
  • adding less deactivator into the desmearing agent 12 may change the aspect ratio of the via opening 10.
  • adding less deactivator into the desmearing agent 12 may make the via opening 10 wider at the bottom of the opening 10 without widening the top of the via opening 10 (see FIG. 7).
  • fine pitch via openings 10 may benefit from having via openings 10 with larger bottoms in order promote electrical reliability in the electrical component 11.
  • the deactivator may include an antioxidant.
  • the antioxidant may include a substituted phenol or polyethylene glycol. A variety of deactivators are contemplated.
  • FIG. 2 is a flow diagram illustrating an example method [200] of forming a via opening 10 in an electronic component 11.
  • FIG. 4 shows an example via opening 10 before the method [200] is applied to the via opening 10.
  • the method [200] includes [210] inserting a desmearing agent 12 into a via opening 10 in a dielectric layer 16 to remove smear 13 from the via opening 10.
  • the desmearing agent includes a first species which forms radicals when coming into contact with a conductor 14 (e.g., copper) within the via opening 10.
  • the radical activates an inactive second species to form an active second species 15 that is part of the desmearing agent 12 (see FIG. 5).
  • the active second species 15 converts smear to solubilized reaction products within the via opening 10.
  • the method [200] includes [220] inserting an active third species into the via opening 10 together with the desmearing agent 12 which may allow the active third species to roughen the via opening 10 and an outer surface 19 of the dielectric layer 17. It should be noted that roughening the outer surface 19 may promote adhesion with another conductor 14 that forms the next layer.
  • FIGS. 8-10 This process of roughening the via opening 10 and the outer surface 19 is illustrated in FIGS. 8-10.
  • FIG. 8 shows the example via opening 10 and outer surface 19 before a desmearing agent 12 that includes an active third species has been inserted into the via opening 10.
  • FIG. 9 shows the via opening 10 and outer surface 19 of FIG. 8 after the desmearing agent 12 that includes an active third species has been inserted into the via opening 10 to roughen the via opening 10 and the outer surface 19.
  • FIG. 10 shows the via opening 10 of FIG.
  • the method [200] further includes [230] rinsing the via opening
  • the active third species may include a metal with a chemical potential that is sufficient to oxidize the dielectric layer.
  • the active third species may be similar to the active second species.
  • FIG. 3 is a flow diagram illustrating an example method [300] of forming a via opening 10 in an electronic component 11.
  • FIG. 4 shows an example via opening 10 before the method [300] is applied to the via opening 10.
  • the method [300] includes [310] inserting a desmearing agent 12 into a via opening 10 to remove smear 13 from the via opening 10.
  • the desmearing agent 12 includes an alkyl halide which forms radicals R° when coming into contact with copper within the via opening 10.
  • the radicals R° activate an inactive manganate to form an active manganate 15 that is part of the desmearing agent 12.
  • the active manganate 15 converts the smear 13 to carbonate within the via opening 10.
  • the method [300] further includes [330] rinsing the via opening
  • the via opening 10 may be rinsed with an acidic solution 18.
  • inserting a desmearing agent 12 into a via opening 10 to remove smear 13 from the via opening 10 includes inserting the electrical component 11 into a chemical bath. It should be noted other forms of inserting the desmearing agent 12 into the via opening 10 are contemplated.
  • radicals are initially generated using an alkyl halide (RX) which reacts with the exposed Cu surface to form a radical (R°) and Cu halide (CuX) (see equation 6 below).
  • RX alkyl halide
  • CuX Cu halide
  • the radical R° then extracts an electron from Mn0 4 2 ⁇ forming the active permanganate Mn0 4 " (see equation 7 below).
  • the active permanganate would then oxidize the smear using the mechanism shown in equation 8.
  • Formation of radicals R° from alkyl halides over Cu(0) requires that the R group must be chosen to have the appropriate electrochemical potential to oxidize Mn0 4 2 ⁇ .
  • the methods [100], [200], [300] described herein may widen via bottoms to improve via reliability with electronic components.
  • the methods [100], [200], [300] may also allow for a reduction in the laser shot count that is typically used to create vias. Reducing laser shot count may increase manufacturing throughput and reduce capital costs associated with purchasing lasers.
  • FIG. 11 is a block diagram of an electronic apparatus 1100 incorporating at least one method [100], [200], [300] described herein.
  • Electronic apparatus 1100 is merely one example of an electronic apparatus in which the method [100], [200], [300] may be used.
  • Examples of an electronic apparatus 1100 include, but are not limited to, personal computers, tablet computers, mobile telephones, game devices, MP3 or other digital music players, etc.
  • electronic apparatus 1100 comprises a data processing system that includes a system bus
  • System bus 1102 provides communications links among the various components of the electronic apparatus 1100 and may be implemented as a single bus, as a combination of busses, or in any other suitable manner.
  • the electronic assembly 1110 may include any circuit or combination of circuits.
  • the electronic assembly 1110 includes a processor 1112 which can be of any type.
  • processor means any type of
  • computational circuit such as but not limited to a microprocessor, a
  • CISC complex instruction set computing
  • RISC reduced instruction set computing
  • VLIW very long instruction word
  • DSP digital signal processor
  • circuits that may be included in electronic assembly 1110 are a custom circuit, an application-specific integrated circuit (ASIC), or the like, such as, for example, one or more circuits (such as a communications circuit 1114) for use in wireless devices like mobile telephones, tablet computers, laptop computers, two-way radios, and similar electronic systems.
  • ASIC application-specific integrated circuit
  • the IC can perform any other type of function.
  • the electronic apparatus 1100 may also include an external memory 1120, which in turn may include one or more memory elements suitable to the particular application, such as a main memory 1122 in the form of random access memory (RAM), one or more hard drives 1124, and/or one or more drives that handle removable media 1126 such as compact disks (CD), flash memory cards, digital video disk (DVD), and the like.
  • a main memory 1122 in the form of random access memory (RAM)
  • hard drives 1124 and/or one or more drives that handle removable media 1126 such as compact disks (CD), flash memory cards, digital video disk (DVD), and the like.
  • removable media 1126 such as compact disks (CD), flash memory cards, digital video disk (DVD), and the like.
  • the electronic apparatus 1100 may also include a display device
  • keyboard and/or controller 1130 which can include a mouse, trackball, touch screen, voice-recognition device, or any other device that permits a system user to input information into and receive information from the electronic apparatus 1100.
  • Example 1 includes a method of forming a via opening in an electric component.
  • the method includes inserting a desmearing agent into a via opening to remove smear from the via opening.
  • the desmearing agent includes a first species which forms radicals when coming into contact with a conductor within the via opening.
  • the radical activates an inactive second species to form an active second species that is part of the desmearing agent.
  • the active second species converts smear to solubilized reaction products within the via opening.
  • the method further includes rinsing the via opening to remove the desmearing agent and the solubilized reaction products from the via opening.
  • Example 2 includes the method of example 1, wherein inserting a desmearing agent into a via opening to remove smear from the via opening includes inserting the electrical component into a chemical bath.
  • Example 3 includes the method of any one of examples 1-2, wherein the conductor is copper.
  • Example 4 includes the method of any one of examples 1-3, wherein the inactive second species may have an electrochemical potential such that the inactive second species does not oxidize the smear.
  • Example 5 includes the method of any one of examples 1-4, wherein the active second species may have an electrochemical potential such that the active second species oxidizes the smear.
  • Example 6 includes the method of any one of examples 1-5, wherein rinsing the via opening to remove the desmearing agent and solubilized reaction products from the electrical component includes rinsing the via opening with an acidic solution.
  • Example 7 includes the method of any one of examples 1-6, wherein the desmearing agent includes a deactivator that makes some of the radicals in the first species inactive in order to control a width of the via opening.
  • Example 8 includes the method of any one of examples 1-7, wherein adding more deactivator into the desmearing agent reduces the effect of the radicals on the via opening.
  • Example 9 includes the method of any one of examples 7-8, wherein adding less deactivator into the desmearing agent increases the effect of the radicals on the via opening.
  • Example 10 includes the method of example 9, wherein adding less deactivator into the desmearing agent changes the aspect ratio of the via opening.
  • Example 11 includes the method of any one of examples 9-10, wherein adding less deactivator into the desmearing agent makes the via opening wider, wherein the desmearing agent makes the via opening wider at the bottom without making the via opening wider at the top.
  • Example 12 includes the method of any one of examples 1-11, wherein the deactivator includes an antioxidant.
  • Example 13 includes the method of examples 12, wherein the antioxidant includes a substituted phenol or polyethylene glycol.
  • Example 14 includes a method of forming a via opening in an electric component.
  • the method includes inserting a desmearing agent into a via opening in a dielectric layer to remove smear from the via opening, wherein the desmearing agent includes a first species which forms radicals when coming into contact with a conductor within the via opening.
  • the radical activates an inactive second species to form an active second species that is part of the desmearing agent.
  • the active second species converts smear to solubilized reaction products within the via opening.
  • the method further includes inserting an active third species into the desmearing agent before the desmearing agent is inserted into the via opening such that the active third species roughens the via opening and an outer surface of the dielectric layer when the desmearing agent is inserted into the via opening and on the outer surface of the dielectric layer.
  • the method further includes rinsing the via opening to remove the desmearing agent and the solubilized reaction products from the via opening.
  • Example 15 includes the method of example 14, wherein roughening the via opening promotes adhesion with another conductor that fills the via opening.
  • Example 16 includes the method of any one of examples 14-15, wherein the active third species includes a metal with a chemical potential that is sufficient to oxidize the dielectric layer.
  • Example 17 includes the method of any one of examples 14-16, wherein the active third species is similar to the active second species.
  • Example 18 includes a method of forming a via opening in an electric component.
  • the method includes inserting a desmearing agent into a via opening to remove smear from the via opening.
  • the desmearing agent includes an alkyl halide which forms radicals when coming into contact with copper within the via opening.
  • the radical activates an inactive manganate to form an active manganate that is part of the desmearing agent.
  • the active manganate converts the smear to carbonate within the via opening.
  • the method further includes rinsing the via opening to remove the desmearing agent and the carbonate from the via opening.
  • Example 19 includes the method of example 18, wherein rinsing the via opening to remove the desmearing agent and carbonate from the electrical component includes rinsing the via opening with an acidic solution.
  • Example 20 includes the method of any one of examples 18-19, wherein inserting a desmearing agent into a via opening to remove smear from the via opening includes inserting the electrical component into a chemical bath.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Printing Elements For Providing Electric Connections Between Printed Circuits (AREA)

Abstract

Selon certains exemples, l'invention concerne un procédé de formation d'une ouverture de trou d'interconnexion dans un composant électrique. Le procédé comprend l'insertion d'un agent de déglaçage dans une ouverture de trou d'interconnexion pour enlever la coulée de résine de l'ouverture de trou d'interconnexion. L'agent de déglaçage comprend une première espèce qui forme des radicaux lorsqu'elle entre en contact avec un conducteur à l'intérieur de l'ouverture de trou d'interconnexion. Le radical active une seconde espèce inactive pour former une seconde espèce active qui est une partie de l'agent de déglaçage. La seconde espèce active convertit la coulée de résine en produits de réaction solubilisés à l'intérieur de l'ouverture de trou d'interconnexion. Le procédé comprend en outre le rinçage de l'ouverture de trou d'interconnexion pour éliminer de l'ouverture de trou d'interconnexion l'agent de déglaçage et les produits de réaction solubilisés.
PCT/US2015/047795 2015-08-31 2015-08-31 Procédé de formation d'une ouverture de trou d'interconnexion Ceased WO2017039624A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/US2015/047795 WO2017039624A1 (fr) 2015-08-31 2015-08-31 Procédé de formation d'une ouverture de trou d'interconnexion

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2015/047795 WO2017039624A1 (fr) 2015-08-31 2015-08-31 Procédé de formation d'une ouverture de trou d'interconnexion

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WO2017039624A1 true WO2017039624A1 (fr) 2017-03-09

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020151177A1 (en) * 2001-04-12 2002-10-17 Cabot Microelectrics Corporation Method of reducing in-trench smearing during polishing
US20030036269A1 (en) * 2001-08-08 2003-02-20 Toshihisa Shimo Method of removing smear from via holes
US20120144667A1 (en) * 2007-06-06 2012-06-14 Ddi Global Corp. Multilayer printed wiring boards with holes requiring copper wrap plate
US20130199830A1 (en) * 2010-08-10 2013-08-08 Hitachi Chemical Company Ltd Resin composition, cured resin product, wiring board, and manufacturing method for wiring board
US20130247373A1 (en) * 2012-03-09 2013-09-26 Mitsui Mining & Smelting Co., Ltd. Method of producing printed wiring board and copper foil for laser processing

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020151177A1 (en) * 2001-04-12 2002-10-17 Cabot Microelectrics Corporation Method of reducing in-trench smearing during polishing
US20030036269A1 (en) * 2001-08-08 2003-02-20 Toshihisa Shimo Method of removing smear from via holes
US20120144667A1 (en) * 2007-06-06 2012-06-14 Ddi Global Corp. Multilayer printed wiring boards with holes requiring copper wrap plate
US20130199830A1 (en) * 2010-08-10 2013-08-08 Hitachi Chemical Company Ltd Resin composition, cured resin product, wiring board, and manufacturing method for wiring board
US20130247373A1 (en) * 2012-03-09 2013-09-26 Mitsui Mining & Smelting Co., Ltd. Method of producing printed wiring board and copper foil for laser processing

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