Selective dry etching of tantalum nitride
Abstract
The invention describes a method for the selective dry etching of tantalum and tantalum nitride films. Tantalum nitride layers (30) are often used in semiconductor manufacturing. The semiconductor substrate is exposed to a reducing plasma chemistry which passivates any exposed copper (40). The tantalum or tantalum nitride films are selectively removed using an oxidizing plasma chemistry.

Term
Term ended
Projected expiry passed 23 September 2023, 3 years ago.
- Priority
- Filed
- Published
- Projected expiry
- Today
9 claims: 2 independent, 7 dependent
- 1A method to selectively etch tantalum nitride, comprising:providing a semiconductor substrate comprising at least one tantalum nitride layer;exposing said semiconductor substrate to reducing plasma chemistry wherein said reducing chemistry passivates an exposed copper region;and exposing said tantalum nitride layer to an oxidizing plasma chemistry selectively removing all or a portion of said tantalum nitride layer.
- 5The method claim 3 wherein said gas flow rates of oxygen and tetrafluoroethylene are 1000 Sccm to 5000 Sccm and 20 Sccm to 100 Sccm respectively.
Independent claims2
10 paragraphs in 5 sections, as filed
FIELD OF THE INVENTION
0001The present invention relates to a dry etching process for the selective removal of tantalum and tantalum nitride layers.
BACKGROUND OF THE INVENTION
0002The use of copper for forming the metal interconnect lines in integrated circuits is finding increasing usage due to the superior properties of copper compared to the widely used aluminum lines. One of the primary challenges in integrated circuit fabrication is reducing the RC time delay. An important component of the RC time delay is the resistance and the capacitance present in the metal lines that connect the various devices that comprise the integrated circuit. The resistivity of copper is 1.72 x 10<sup>-6</sup> Ohm -cm versus that of aluminum which is 2.82 x 10<sup>-6</sup> Ohm-cm. This reduced resistivity will reduce the RC delay associated with copper lines. In addition copper has superior resistance to electromigration and higher reliability when compared to commonly used aluminum alloys.
0003In general integrated circuit metal lines are formed in dielectric layers. These dielectric layers typically comprise silicon oxide or contain silicon oxide. In a typical damascene process for forming an integrated circuit copper line a trench is first formed in a dielectric layer which is formed over a silicon substrate containing electronic devices such as transistors, diodes, etc. This is illustrated in Figure 1 where the dielectric layer 10 is formed over a silicon substrate. Using standard silicon processing technology a trench 20 is formed in the dielectric layer 10. Because copper reacts with silicon oxide, it is necessary to confine it using a barrier layer. A commonly used barrier layer is tantalum nitride (Ta<sub>x</sub>N<sub>y</sub>) which is formed on the dielectric layer before the formation of the copper layer. A Ta<sub>x</sub>N<sub>y</sub> barrier layer 30, 35 is shown in Figure 1. The Ta<sub>x</sub>N<sub>y</sub> is formed in a blanket deposition resulting in region 35 which lines the trench and region 30 which forms on the surface on the dielectric layer 10 outside the trench. Following the formation of the Ta<sub>x</sub>N<sub>y</sub> barrier layer a thick layer of copper is formed. Using standard processing techniques such as chemical mechanical processing (CMP) the excess copper is removed leaving that portion of copper 40 which forms in the trench. To complete the process the portions of the barrier layer which are not cover by copper (i.e. regions 30 in Figure 1) must be removed. Using existing methods the selective removal of the Ta<sub>x</sub>N<sub>y</sub> layer is a very difficult process. CMP processes are often used to remove the exposed Ta<sub>x</sub>N<sub>y</sub> layer 30 but this often results in dishing of the exposed copper surface and erosion of the underlying dielectric layer 10. Wet chemical etching of the exposed Ta<sub>x</sub>N<sub>y</sub> layer is difficult because most of the chemical solutions which etch Ta<sub>x</sub>N<sub>y</sub> will attack the underlying dielectric material and etch or damage the exposed copper surfaces. A method is therefore needed to selectively etch Ta<sub>x</sub>N<sub>y</sub> layers without damaging the underlying dielectric layer and/or the exposed copper surface.
SUMMARY OF INVENTION
0004Tantalum and tantalum nitride layers are often formed during integrated circuit formation. The present invention provides a method to selectively etch tantalum nitride. The present invention comprises exposing a semiconductor substrate comprising at least one tantalum layer and/or tantalum nitride layer to reducing plasma chemistry where this reducing chemistry passivates any exposed copper or dielectric layers exposed to the reducing chemistry. All or a portion of the tantalum and/or tantalum nitride layers can then be selectively removed by exposing the semiconductor substrate to an oxidizing plasma chemistry.
BRIEF DESCRIPTION OF THE DRAWINGS
0005In the drawings: FIGURE 1 is a cross section diagram illustrating a tantalum nitride barrier layer beneath a copper region.
DETAILED DESCRIPTION OF THE INVENTION
0006A two step dry etch process is used to selectively etch Ta<sub>x</sub>N<sub>y</sub> and/or Tantalum (Ta). The subscripts x and y in the chemical symbol for tantalum nitride (i.e. Ta<sub>x</sub>N<sub>y</sub>) represent integer numbers that depend on the form of the tantalum nitride alloy. The etch process of the present invention will selectively etch all forms of tantalum nitride alloys and well as tantalum metal. The process conditions are described in the following table: <tables id="tabl0001" num="0001"><img file="EP1401015A1_D0001.tif" /></tables>
0007As shown in above table, the first step of the process comprises a plasma process with nitrogen (N<sub>2</sub>) and ammonium (NH<sub>3</sub>) as the active gases. In addition to N<sub>2</sub> and NH<sub>3</sub> other gases, including carrier gases such as argon, can be present in the chamber without departing from the present invention. In an embodiment of the present invention the flow rates of N<sub>2</sub> and NH<sub>3</sub> are preferably 480 Sccm and 2200 Sccm respectively, the power 900 Watts, and the wafer temperature approximately 250°C. This step modifies the surfaces of the Ta<sub>x</sub>N<sub>y</sub> and/or Ta layers by exposing the surfaces to a reducing plasma chemistry. In addition to modifying the surface of the Ta<sub>x</sub>N<sub>y</sub> and/or Ta, the first step of the process passivates the copper surfaces exposed to the first step (e.g. 40 in Figure 1) thereby reducing the oxidation rate of the copper surface. Therefore the first step of the etch process simultaneously modifies the surface of the Ta<sub>x</sub>N<sub>y</sub> and/or Ta layers and passivates the exposed copper surfaces reducing the oxidation rate of the copper surface.
0008The second step of the process comprises a plasma process with oxygen (O<sub>2</sub>) and tetrafluoroethylene (C<sub>2</sub>F<sub>4</sub>) as the active gases. In addition to O<sub>2</sub> and C<sub>2</sub>F<sub>4</sub> other gases can be present in the chamber without departing from the instant invention. In an embodiment of the instant invention the flow rates of O<sub>2</sub> and C<sub>2</sub>F<sub>4</sub> are preferably 2900 Sccm and 60 Sccm respectively, the power 1200 Watts, and the wafer temperature approximately 60°C. This step uses an oxidizing plasma chemistry to remove the modified Ta<sub>x</sub>N<sub>y</sub> and/or Ta layer without significantly attacking the dielectric layer. In addition the passivated copper surface from step one will be highly resistant to the oxidizing chemistry of the second step and therefore will not be significantly attacked during step two of the process. The two step etch process of the instant invention therefore results in a selective process for etching (or removing) Ta<sub>x</sub>N<sub>y</sub> and/or Ta layers without attacking any underlying dielectric layers or exposed copper surfaces.
0009The above described two step etch process can be performed in the same plasma chamber or may be performed in separate chambers. In addition to etching the Ta<sub>x</sub>N<sub>y</sub> and/or Ta barrier layers in copper metallization process, the process of the instant invention can be used to etch Ta<sub>x</sub>N<sub>y</sub> and/or Ta layers and films in any application.
0010While this invention has been described with reference to illustrative embodiments, this description is not intended to be construed in a limiting sense. Various modifications and combinations of the illustrative embodiments, as well as other embodiments of the invention will be apparent to persons skilled in the art upon reference to the description. It is therefore intended that the appended claims encompass any such modifications or embodiments.
Contents5
3 sheets
Sheet 1 Sheet 2 Sheet 3
Every citation, both ways
| Document | Relation | Office | Category | Cited during | Relevant claims |
|---|---|---|---|---|---|
| US9806023B1 | Cited by | United States of America | – | Applicant | – |
| US9917137B1 | Cited by | United States of America | – | Applicant | – |
| US10431464B2 | Cited by | United States of America | – | Applicant | – |
| US10741397B2 | Cited by | United States of America | – | Applicant | – |
| US9685406B1 | Cited by | United States of America | – | Applicant | – |
| US10002831B2 | Cited by | United States of America | – | Applicant | – |
| US10319783B2 | Cited by | United States of America | – | Applicant | – |
| EP0793271A2 | Cites | European Patent Office (EPO) | – | Applicant | – |
| EP1156133A2 | Cites | European Patent Office (EPO) | X | Search report | 1 |
| US6086777A | Cites | United States of America | X | Search report | 1 |
| US6329276B1 | Cites | United States of America | – | Applicant | – |
| US6331380B1 | Cites | United States of America | A | Search report | 1-9 |
| US6331380B1 | Cites | United States of America | A | Search report | 1-9 |
| IBBOTSON D E ET AL: "SELECTIVE INTERHALOGEN ETCHING OF TANTALUM COMPOUNDS AND OTHER SEMICONDUCTOR MATERIALS", APPLIED PHYSICS LETTERS, AMERICAN INSTITUTE OF PHYSICS. NEW YORK, US, vol. 46, no. 8, 15 April 1985 (1985-04-15), pages 794 - 796, XP000816727, ISSN: 0003-6951 | Non-patent | – | – | Search report | – |
45 members in 9 offices; this record represents the family
Priority claims2
| Document | Office | Kind | Date |
|---|---|---|---|
| 253791 | United States of America | – | |
| 25379102 | United States of America | A |
Members45
| Document | Office | Kind | |
|---|---|---|---|
| CA2191437A1 | Canada | A1 | |
| CA2440657A1 | Canada | A1 | |
| CA2440662A1 | Canada | A1 | |
| CA2440667A1 | Canada | A1 | |
| WO9534149A1 | World Intellectual Property Organization (WIPO) | A1 | |
| AU2696295A | Australia | A | |
| US5557612A | United States of America | A | |
| FI964805A0 | Finland | A0 | |
| FI964805A | Finland | A | |
| FI964805A7 | Finland | A7 | |
| EP0763295A1 | European Patent Office (EPO) | A1 | |
| US5625651A | United States of America | A | |
| US5644573A | United States of America | A | |
| KR970703664A | Republic of Korea | A | |
| JPH10503893A | Japan | A | |
| AU695092B2 | Australia | B2 | |
| AU8946798A | Australia | A | |
| US5933454A | United States of America | A | |
| AU738026B2 | Australia | B2 | |
| US2002090008A1 | United States of America | A1 | |
| US2002093989A1 | United States of America | A1 | |
| US2002122437A1 | United States of America | A1 | |
| US2002131455A1 | United States of America | A1 | |
| EP0763295B1 | European Patent Office (EPO) | B1 | |
| US6473438B1 | United States of America | B1 | |
| DE69528646D1 | Germany | D1 | |
| DE69528646T2 | Germany | T2 | |
| KR100380644B1 | Republic of Korea | B1 | |
| CA2191437C | Canada | C | |
| EP1401015A1This record | European Patent Office (EPO) | A1 | |
| US2004058528A1 | United States of America | A1 | |
| JP2004119977A | Japan | A | |
| US2004253812A1 | United States of America | A1 | |
| US6937623B2 | United States of America | B2 | |
| US6939795B2 | United States of America | B2 | |
| US2005245088A1 | United States of America | A1 | |
| US2005250337A1 | United States of America | A1 | |
| US6979648B2 | United States of America | B2 | |
| US7068678B2 | United States of America | B2 | |
| US7079549B2 | United States of America | B2 | |
| US7110370B2 | United States of America | B2 | |
| US7250372B2 | United States of America | B2 | |
| US7354853B2 | United States of America | B2 | |
| EP1401015B1 | European Patent Office (EPO) | B1 | |
| DE60330426D1 | Germany | D1 |
27 legal events, as 4 offices reported them to INPADOC
Over the term
Point at a mark for the eventEvents
| Event | Code | Office | |
|---|---|---|---|
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Gb: european patent ceased through non-payment of renewal feeCeasedGBPC | GBPC | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Application deemed withdrawn, or ip right lapsed, due to non-payment of renewal feeWithdrawnR119 | R119 | DE | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Fee paymentPLFP | PLFP | FR | |
| Fee paymentPLFP | PLFP | FR | |
| Fee paymentPLFP | PLFP | FR | |
| No opposition filedOpposition26N | 26N | EP | |
| No opposition filed within time limitOppositionORIGINAL CODE: 0009261PLBE | PLBE | EP | |
| Information on the status of an ep patent application or granted ep patentGrantedSTATUS: NO OPPOSITION FILED WITHIN TIME LIMITSTAA | STAA | EP | |
| Corresponds to:REF | REF | EP | |
| Designated contracting statesAK | AK | EP | |
| European patent grantedGrantedFG4D | FG4D | GB | |
| (expected) grantORIGINAL CODE: 0009210GRAA | GRAA | EP | |
| Grant fee paidORIGINAL CODE: EPIDOSNIGR3GRAS | GRAS | EP | |
| Title (correction)SELECTIVE DRY ETCHING OF TANTALUM NITRIDERTI1 | RTI1 | EP | |
| Despatch of communication of intention to grant a patentORIGINAL CODE: EPIDOSNIGR1GRAP | GRAP | EP | |
| First examination report despatched17Q | 17Q | EP | |
| Designation fees paidAKX | AKX | EP | |
| Request for examination filed17P | 17P | EP | |
| Designated contracting statesAK | AK | EP | |
| Request for extension of the european patentAX | AX | EP | |
| Public reference made under article 153(3) epc to a published international application that has entered the european phaseORIGINAL CODE: 0009012PUAI | PUAI | EP |
Numbers
- Publication
- 1401015
- Application
- 31035223
Titles3
- German
- Selektive Trockenätzung von Tantal und Tantalnitrid
- English
- Selective dry etching of tantalum and tantalum nitride
- French
- Gravure sèche sélective de tantale et nitrure de tantale
Classification
- CPC, 8
- H10W20/033
- C23F4/00
- H10P95/04
- H10P50/267
- H10W20/062
- H10W20/031
- H10W20/0523
- H10W20/054
- IPC, 2
- C23F4 00
- H10P14 40
Designated states2
- Contracting states, 1
- Türkiye
- Extension states, 1
- North Macedonia