EP1218569B1 - Galvanisierungslösung für die galvanische abscheidung von kupfer - Google Patents

Galvanisierungslösung für die galvanische abscheidung von kupfer Download PDF

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Publication number
EP1218569B1
EP1218569B1 EP00962386A EP00962386A EP1218569B1 EP 1218569 B1 EP1218569 B1 EP 1218569B1 EP 00962386 A EP00962386 A EP 00962386A EP 00962386 A EP00962386 A EP 00962386A EP 1218569 B1 EP1218569 B1 EP 1218569B1
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EP
European Patent Office
Prior art keywords
copper
deposition
film
galvanic
current
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.)
Expired - Lifetime
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EP00962386A
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German (de)
English (en)
French (fr)
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EP1218569A1 (de
Inventor
Jung-Chih Hu
Wu-Chun Gau
Ting-Chang Chang
Ming-Shiann Feng
Chun-Lin Cheng
You-Shin Lin
Ying-Hao Li
Lih-Juann Chen
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BASF SE
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Merck Patent GmbH
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper

Definitions

  • the present invention relates to a new electroplating solution for the galvanic deposition of Copper. Hydroxylamine sulfate or Hydroxylamine hydrochloride used as additive reagents and that in the galvanic deposition of copper electroplating solution used in semiconductor production added.
  • Copper is ideal for long and narrow conductor tracks because there is a low resistivity exhibits and good reliability can be expected.
  • the introduction of Cu metallization still has to be done the processing difficulties associated with Cu be overcome.
  • To integrate the Cu metallization in production also need to be commercially mature Plants to be developed first.
  • galvanic deposition is done by galvanic (electrochemical) deposition.
  • the galvanic Separation is an attractive alternative because they are not available for tungsten and aluminum stands.
  • the galvanic deposition is compared to the Vacuum manufacturing technology and for currentless deposition very inexpensive.
  • a number of research groups have galvanic deposition methods for use in Damascene structures developed.
  • the galvanic deposition has the potential disadvantage that it is a two-step process.
  • the germ layer provides a low-resistance conductor for the galvanizing current, that drives the process and makes it easier also film nucleation. If the germ layer is not flawless (i.e. continuous), it can a cavity is created in the copper filling.
  • the copper seed layer plays in the galvanic deposition a critical role in two ways. At the wafer level, the seed layer conducts current from Edge of the wafer to the center, so that you have the electroplating power source just near the edge with the To bring wafers into contact. The seed layer must be so thick that the uniformity of the galvanic Deposition not by voltage drops from Wafer edge is reduced to the middle of the wafer. In one the germ layer conducts electricity from top to bottom of vias and trenches. If the germ layer on the bottom is not thick enough is formed during the deposition in the middle the via or the trench a cavity out. To produce a uniform and good adhesive film made of galvanically deposited copper a germ layer must be faultless over the barrier layer be deposited.
  • PVD copper has a high aspect ratio of Vias and trenches have poor step coverage on, but was used for galvanic deposition successfully applied by Cu. PVD copper is suitable up to the narrowest for the seed layer Structure of 0.3 ⁇ m.
  • the PVD copper seed layer can be below 0.3 ⁇ m with I-PVD process (ionized PVD) be deposited. Also, for the next Generations probably used a CVD seed layer become.
  • Copper CVD is a good alternative for the seed layer represents what's primarily on the step cover based on almost 100%. Superior step coverage of the CVD copper process the PVD process has no additional costs. With the CVD copper seed layer process, this is possible complete filling of narrow vias in a single damascene application, an important one Future technology methods.
  • the galvanic deposition takes place in two Steps, but according to calculations it offers a smaller number entire "Cost of Ownership" (COO) as CVD.
  • COO Cost of Ownership
  • the main difference is primarily on the lower ones Capital and chemical costs in the galvanic Deposition. Most importantly, that with a well-coordinated process for Galvanic deposition structures with a high aspect ratio can fill.
  • the speed of the galvanic deposition depends usually directly dependent on the current density. If on upper part of a structure (or on the upper sharp Edges) a high density and a lower one at the bottom If there is density, you get a different one Plating speed. Cavitation occurs because the galvanization on the top sharp Trench edges faster than on the ground. to Improve deposition uniformity and the gap filling capacity in the galvanic deposition there are physical and chemical ones Method.
  • the physical method uses one pulsed electroplating (PP) or periodic pulse reversal (PPR) with both positive and negative Pulses (e.g. a waveform to the cathode / anode system).
  • Periodic pulsed electroplating (PPR) could reduce cavitation since the metal deposition rate approximately within a trench corresponds in the upper part. These are practically a deposition etch sequence. there a deposition-etching sequence can result, the copper in the high density areas faster removes than in low density areas and that required gap filling capacity results.
  • the pulsed Electroplating (PP) can be the effective thickness of the Reduce mass transfer boundary layer and thus to higher current galvanization current densities as well as better Lead copper distribution. The decreasing thickness of the Boundary layer could decrease considerably Concentration surges lead. Therefore could fill at a high aspect ratio through-hole / trench improved become.
  • the electroplating solution is used for the chemical method organic additives too.
  • a widespread Galvanizing solution consists of many additive groups (e.g. thiourea, acetylthiourea, naphthalenesulfonic acid). However, they serve as smoothing agents Chemicals with amino groups (e.g. tribenzylamine).
  • the Deposition of ductile copper could be done by a Carriers are promoted, whereas brighteners and Smoothing agent non-uniform substrates in the galvanic Smooth deposition.
  • For a very good one galvanic deposition in small dimensions (with very high aspect ratios for future ULSI metallization) one has to go through further investigations gain an understanding of additive reagents.
  • the Determination of suitable reagents for a special one Working method and a suitable concentration ratio often decides on the success of one gap-filling electroplating process.
  • the specific resistance of galvanic deposited copper was less than 1.88 ⁇ ⁇ cm. It it turned out that the filling capacity was high of the uniformity of the sputtered copper in the trenches hung. If the cover is sputtered An essential copper on top of the trench Closure would show up after the Galvanization form large voids. With uniform Sputtering of copper in the trenches would be obtained however, a good copper filling during the electroplating. In addition, inadequate control of the Waveform under the same sputtering and plating conditions lead to strong voids.
  • CuTek Research Inc. developed a new separation system that is a standard Cluster tool configuration with fully automatic Enter the dry and clean wafer and Output of the dry and clean wafer.
  • the Galvanic deposition of Cu takes place on a Cu seed layer with a thickness of 30 to 150 nm.
  • a 30 nm thick sputter layer made of Ta or TaN serves as Barrier or adhesive layer.
  • PP pulsed Electroplating
  • PPR periodic pulse reversal
  • Dual damascene structures with a structure size of 0.4 ⁇ m with an aspect ratio of 5: 1 and deep Contact structures with a structure size of 0.25 ⁇ m with an aspect ratio of 8: 1 could completely are completely filled without voids or joints.
  • the contained in the galvanically deposited Cu film Contamination was less than 50 ppm.
  • Major contaminants were found to be H, S, Cl and C.
  • At the edge of the wafer there is a higher concentration of these Elements as measured in the middle. This is probably due to the strong hydrogen evolution and the stronger incorporation of organic additive in Area due to high current density.
  • CMP chemical-mechanical Polishing
  • the cathode growth is influenced by many factors: (a) the Quality of the anode, (b) the electrolyte composition and the electrolyte impurities, (c) the current density, (d) the surface condition of the starting cathode, (e) the geometry of the anode and cathode, (f) the uniformity the distance (movement) and the distance between the electrodes and (g) the temperature or current density.
  • wafers made of single-crystal silicon with (001) -orientation of the p-type with 15 to 25 ⁇ -cm and a diameter of 6 inches were used as deposition substrates.
  • the bare wafers were first cleaned using a conventional wet cleaning process.
  • the wafers were then treated with a dilute HF solution (1:50) and then placed in a deposition chamber.
  • a 50 nm thick TiN layer was deposited as a diffusion barrier layer and a 50 nm thick Cu layer as a seed layer.
  • Structured wafers were fabricated to investigate the ability to galvanically deposit Cu in small trenches and vias. After standard RCA cleaning, the wafers were subjected to thermal oxidation.
  • a unique dimension of trenches / vias was defined using a reactive ion etching (RIE) photolithographic technique.
  • RIE reactive ion etching
  • a 40 nm thick TaN layer as a barrier layer and a 150 nm thick Cu layer as a seed layer were deposited with IMP-PVD.
  • the size of the trench / via was defined between 0.3 and 0.8 ⁇ m.
  • a galvanizing solution used for the galvanic deposition of Cu usually contained CuSO 4 .5H 2 O, H 2 SO 4 , Cl - , additives and wetting agents.
  • the composition of the galvanizing solution is listed in Table 1. Additives have often been added to the galvanic deposition of Cu because they act as brighteners, hardeners, grain refiners and smoothing agents.
  • the current density applied was 0.1 to 4 A / dm 2 .
  • a Cu (P) material (99.95% Cu, 0.05% P) was used as an anode to provide a sufficient amount of Cu ions, which gave good quality films made of electrodeposited Cu.
  • FESEM Field emission scanning electron microscope
  • the specific resistance of electrodeposited Cu film was measured with a 4-point sensor.
  • the sheet resistance of the Cu films was measured with a Standard probe with four equally spaced Points determined.
  • the distance between sensors with four equally spaced points was 1.016 mm.
  • Current was through the outer two sensors passed and the voltage across the inner two sensors measured. Here, a current of 0.1 to 0.5 mA applied.
  • the stoichiometry and uniformity along the Depth directions were determined using an Auger electron spectroscope certainly.
  • the contamination analysis was carried out using SIMS (secondary ion mass spectrometry) carried out.
  • FIG. 7 shows the relationship between specific film resistance and H 2 SO 4 concentration.
  • the specific resistance remains constant with increasing concentration.
  • SEM images show the film morphology in the presence and absence of H 2 SO 4 . It turns out that the uniformity and roughness of the copper film in the presence of sulfuric acid are smoother and lower the resistivity of the Cu film. It can be assumed that the sulfuric acid prevents polarization of the anode and improves the conductivity of the electrolyte and the cathode film, but does not impair the deposited copper film very much.
  • FIGS. 11 (a) and 11 (b) show the film morphology of Cu electrodeposited on seed layer / TiN / Si at different current densities (1 to 4 A / dm 2 ) without the addition of additives. At high current density, the Cu film is coarse-grained. The specific resistance becomes unusually high ( ⁇ 10 ⁇ mcm) when a large current is applied. The observed high resistivity of the Cu film could be attributed to the formation of a rough surface, which leads to non-conforming films at high currents. The rough surface formed at high current could be explained by the following postulates.
  • the rate of Cu electrodeposition was thought to depend on the diffusion of Cu ions onto the substrate surface.
  • most of the Cu ions had a high electric field; therefore, the diffusion of Cu ions from the solution onto the substrate surface was very fast.
  • the diffusion layer very quickly became depleted of Cu ions; Cu ions could not be replenished immediately from the electroplating solution into the diffusion layer.
  • the galvanic deposition of Cu was limited by the diffusion of Cu ions. This was called diffusion control. Since the Cu ions diffused onto the substrate surface were not replenished, there was no further nucleation on the surface. Rather, Cu aggregation could occur on the surface due to the effect of the large electric field.
  • FIG. 12 shows the relative intensity ratio Cu (111) / Cu (002) determined by means of X-ray diffraction with different applied current densities. According to X-ray diffraction, a strong (111) orientation was always found with a larger current density. The development of the growth orientation of the copper film could be explained by a consideration of the surface energy and shape change energy with different crystal orientation. In the initial phase there was an orientation in the Cu (002) plane because this plane had the lowest surface energy. As the electrical current applied increases, the strain energy becomes a dominant factor in determining grain growth. With large electrical current applied, the peak intensity of Cu (111) increased due to the high strain energy in the Cu (111) orientation.
  • Cu (111) orientation was also preferred because it has better electromigration resistance.
  • Cu (111) formed at high current density could make the surface rougher, as shown in Figure 16 (b).
  • Some additives were added to the electroplating solution to improve the filling during the galvanic deposition of Cu.
  • a Cu film with high resistivity at high current was analyzed by SIMS and compared with that at low current (see FIGS. 13 a and b). The oxygen concentration in the Cu film with high resistivity is higher because it has a rough surface with non-conformity of the film at high current.
  • FIG. 14 shows the recordings of structured wafers galvanic deposition. The Cu seed layer on the bottom and on the side walls is thinner than on the top.
  • FIG. 18 shows the specific resistance of electrodeposited Cu films changes only slightly at a thiourea concentration below 0.054 g / l. In contrast, a high specific resistance is observed at more than 0.054 g / l thiourea.
  • Figure 19 shows the SEM uptake of Cu (111) with 0.03 g / l thiourea addition. The current applied is 2.4 A / dm 2 .
  • FIG. 20 shows the SEM image of electrodeposited Cu film with 0.054 g / l thiourea addition. The current applied is still kept at 2.4 A / dm 2 .
  • the dendrite formation during the electrodeposition of Cu increases with increasing thiourea concentration. This dendrite has a geometric structure similar to that of diffusion-controlled clusters. Thiourea could also decompose into a harmful product (NH 4 SCN), which leads to the embrittlement of galvanically deposited Cu films.
  • Figure 21 shows the change in resistivity of the Cu film with the deposition time.
  • the specific resistance is lower with copper film deposited in large blocks. Therefore, the grain boundary of the copper film decreases, making the surface smoother than that of the initial thin film.
  • the resistivity of the Cu film is higher when thiourea is added.
  • FIG. 22 (a) (b) (c)] the concentration of element S increases with increasing thiourea concentration. It is believed that thiourea adsorbed on the surface of the cathode could cause the increase in resistivity of Cu. In addition, voids are formed when using thiourea as an additive reagent.
  • PEG polyethylene glycol
  • MW> 200 the electrolyte with HCl and a small amount Thiourea (0.0036 g / l) added as a small Amount of thiourea the (111) plane formation could support. It turned out that a higher molecular weight (MW> 200) to a larger one resistivity of the copper film. According to Figure 23 takes the resistance of the copper film with it increasing PEG molecular weight over the Deposition time too. It is believed that the longer one Chain length with thiourea on the substrate surface is absorbed.
  • a common conventional additive reagent for galvanic Deposition of Cu is also glucose.
  • the filling capacity in vias and trenches is however bad. Admittedly forms at all points structure the same thickness, but appears there is still a cavity in the trench.
  • the electrodeposition of Cu with the addition of hydroxylamine sulfate is investigated to determine whether hydroxylamine sulfate could act as a gap filling promoter.
  • the test is carried out with substrates with a via / trench width of 0.3 to 0.8 ⁇ m. Since the thickness of the base layer (seed layer and diffusion barrier) is 60 nm on the bottom and the side walls and 120 nm on the top, a width of less than 0.25 ⁇ m could be galvanically deposited in the 0.35 ⁇ m wide trench. As FIG. 27 shows, cavities are formed without adding additives to the solution.
  • the trench dimension is determined in FIG. 31 to be 0.4 ⁇ m.
  • hydroxylamine sulfate (NH 2 OH) 2 .H 2 SO 4 has both amino and sulfate groups as functional groups, it is proposed as a gap filling promoter to support the electrodeposition of Cu.
  • Another additive reagent namely hydroxylamine hydrochloride (NH 2 OH) ⁇ HCl, is also suitable for the electrodeposition of Cu, since it has a similar functional amino group in connection with chloride.
  • different amounts of hydroxylamine hydrochloride (NH 2 OH) ⁇ HCl were used as the gap filling promoter.
  • the filling capacity is not really good. Some trenches can be completely filled with Cu, but others cannot. However, the lower specific resistance of the copper film could be reduced to 1.9 ⁇ ⁇ cm when using small amounts of hydroxylamine hydrochloride in the electrolyte compared to the copper film without the addition of electrolyte [FIG. 30].
  • a strong Cu (111) peak was observed with a larger current applied.
  • the development of the growth orientation of the copper film could be explained by a consideration of the surface energy and shape change energy with different crystal orientation. In the initial phase there was an orientation in the Cu (002) plane because this plane had the lowest surface energy. As the electrical current applied increases, the strain energy becomes a dominant factor in determining grain growth. A large Cu (111) peak appeared with increasing electrical current. Additives also played an important role in controlling the orientation of the electrodeposited Cu films at low current density. No cavitation was observed in the electrodeposition of Cu in a 0.3 ⁇ m wide trench in the presence of the additive (NH 2 OH) 2 ⁇ H 2 SO 4 . The measured O concentration in the sample was quite low.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Electrodes Of Semiconductors (AREA)
EP00962386A 1999-09-01 2000-08-25 Galvanisierungslösung für die galvanische abscheidung von kupfer Expired - Lifetime EP1218569B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19941605A DE19941605A1 (de) 1999-09-01 1999-09-01 Galvanisierungslösung für die galvanische Abscheidung von Kupfer
DE19941605 1999-09-01
PCT/EP2000/008312 WO2001016403A1 (de) 1999-09-01 2000-08-25 Galvanisierungslösung für die galvanische abscheidung von kupfer

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EP1218569B1 true EP1218569B1 (de) 2003-02-26

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US (1) US6858123B1 (zh)
EP (1) EP1218569B1 (zh)
JP (1) JP4416979B2 (zh)
KR (1) KR100737511B1 (zh)
AT (1) ATE233330T1 (zh)
AU (1) AU7413600A (zh)
DE (2) DE19941605A1 (zh)
MY (1) MY124024A (zh)
TW (1) TWI230208B (zh)
WO (1) WO2001016403A1 (zh)

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EP1308541A1 (en) * 2001-10-04 2003-05-07 Shipley Company LLC Plating bath and method for depositing a metal layer on a substrate
US20050095854A1 (en) * 2003-10-31 2005-05-05 Uzoh Cyprian E. Methods for depositing high yield and low defect density conductive films in damascene structures
JP4540981B2 (ja) * 2003-12-25 2010-09-08 株式会社荏原製作所 めっき方法
DE102006060205B3 (de) * 2006-12-18 2008-04-17 Forschungszentrum Jülich GmbH Verfahren zur Herstellung von Durchkontaktierungen und Leiterbahnen
KR101135332B1 (ko) * 2007-03-15 2012-04-17 닛코킨조쿠 가부시키가이샤 구리전해액 및 그것을 이용하여 얻어진 2층 플렉시블 기판
JP4682285B2 (ja) * 2007-08-30 2011-05-11 日立電線株式会社 配線及び層間接続ビアの形成方法
US8110500B2 (en) * 2008-10-21 2012-02-07 International Business Machines Corporation Mitigation of plating stub resonance by controlling surface roughness
KR101585200B1 (ko) * 2014-09-04 2016-01-15 한국생산기술연구원 동도금액 조성물 및 이를 이용한 동도금 방법
CN115787007A (zh) * 2022-11-03 2023-03-14 厦门大学 一种酸性硫酸盐电子电镀铜添加剂组合物及其应用
CN116682785B (zh) * 2023-08-03 2023-12-29 上海电子信息职业技术学院 一种采用葡萄糖实现tsv完全填充方法

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JPS5757882A (en) * 1980-09-25 1982-04-07 Nippon Mining Co Ltd Black or blue rhodium coated articles, production thereof and plating bath used therefor
DE3619385A1 (de) * 1986-06-09 1987-12-10 Elektro Brite Gmbh Saures sulfathaltiges bad fuer die galvanische abscheidung von zn-fe-legierungen
US5051154A (en) 1988-08-23 1991-09-24 Shipley Company Inc. Additive for acid-copper electroplating baths to increase throwing power
US5174886A (en) * 1991-02-22 1992-12-29 Mcgean-Rohco, Inc. High-throw acid copper plating using inert electrolyte
GB2266894A (en) * 1992-05-15 1993-11-17 Zinex Corp Modified tin brightener for tin-zinc alloy electroplating bath

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WO2001016403A1 (de) 2001-03-08
JP2003508630A (ja) 2003-03-04
ATE233330T1 (de) 2003-03-15
EP1218569A1 (de) 2002-07-03
JP4416979B2 (ja) 2010-02-17
DE50001349D1 (de) 2003-04-03
KR100737511B1 (ko) 2007-07-09
MY124024A (en) 2006-06-30
KR20020029933A (ko) 2002-04-20
DE19941605A1 (de) 2001-03-15
US6858123B1 (en) 2005-02-22
AU7413600A (en) 2001-03-26
TWI230208B (en) 2005-04-01

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