The present invention relates to electroplating an electrically conductive material such as a relatively low resistive metal and especially copper onto a platable resistive metal barrier layer or stack of layers. More particularly, the present invention relates to an apparatus for directly plating onto the resistive metal without the need of a seed or catalyst layer, and especially without the need of a copper seed layer (even though a thin seed may be present, e.g. about 1.ANG.-about 10.ANG.). The present invention makes it possible to form a continuous and relatively uniform layer by growing a thin film from the edge of the surface to be plated towards its center by controlling the conditions of the current or voltage being applied.
The current damascene plating process and especially that for copper requires a copper seed as a conductive layer on top of the highly resistive barrier liner which covers the underlying substrate such as a patterned wafer. The continuous miniaturization of ULSI technology will eventually require the elimination of this copper seed layer. Without this conductive seed, an applied current or voltage will drop off drastically within a short distance from the edge where the electrical contact is made (as will be described below.) As a result of this so-called terminal effect, a sufficient overpotential, η, for copper deposition will only exist near the edge of the substrate and plating is observed at the edge of the substrate only. When applied current is based on the total area of the substrate the effective current density for the perimeter ring is much higher and as a result burned, powdery deposits may be obtained.
Conventional methods to overcome the terminal effects for thin seed layers such as low plating current, segmented anode configuration, high copper concentration and low conductivity (low acid concentration) copper plating baths improve the current distribution and result in a more uniform film thickness. However, these methods apply only in the case where a sufficient plating overpotential exists over the whole substrate surface, from edge to center. For very thin seed layers and more importantly in the absence of a seed layer, the terminal effect of the resistive liner or seed causes such a drastic increase in the potential of the liner material, Um(r), from the edge (r=r0) to center (r=0) of the wafer, that the overpotential, η, becomes zero at a certain distance from the electrical contact and no further plating can occur:
η=Ueq,Cu2+Cu−Um(r) (1)
with Ueq,cu2+/Cu the equilibrium potential (Nernst potential) for copper deposition.
Copper deposition will proceed when η>0, i.e. when Um(r)<Ueq,Cu2+/Cu. In the case of thin copper seeds (5-50 nm), the sheet resistance is still low enough to ensure deposition over the whole substrate surface, although with a non-uniform growth rate in the case of a primary current distribution. In contrast, in the case of highly resistive liner, the drop-off in the overpotential is much more severe and becomes zero at a certain distance, x=r0−r, from the edge of the wafer. In this case, deposition is only observed at the edge of the wafer. Additionally, too low current or overpotential results in a low density of nucleation sites leading to powdery, poorly adherent deposits.
As with copper, the principle of seedless plating holds for the deposition of any conductive material (metal, compound, alloy, composite, semi-metal or semiconductor) onto a resistive substrate.
The present invention provides an apparatus for electroplating a conductive material, such as copper, on a liner or substrate. The apparatus includes:
(a) at least one auxiliary electrode, wherein the at least one auxiliary electrode provides a counter electrode to the liner or substrate, wherein the liner or substrate acts as a first electrode;
(b) a programmable power supply providing for the generation of a current between the at least one auxiliary electrode and the liner or substrate, allowing for the conductive material to be electroplated onto the liner or substrate, and further providing for the adjustment of the current as a function of the change in the area of the conductive material as it is electroplated on the liner or substrate;
(c) a measuring device to detect the propagation of the front of the electroplated material over the surface of the liner or substrate; and
(d) a computer to process the output of the measuring device and calculate a new current to be applied by the programmable power supply as a function of the output of the measuring device.
The measuring device of the apparatus is not limited and can include one or more reference electrodes, a light source (such as a laser or light-emitting diode) and at least one photo detector (such as a photodiode) to measure the reflectivity of the at least one light source, an alternating current or voltage generator and analyzer (such as a frequency response analyzer (FRA) or Lock-in amplifier) to measure the electrochemical impedance of the system, and/or an alternating electromagnetic field generator and sensor for Eddy-current measurements.
The present invention further relates to methods of using the apparatus of the invention.
These and other features of the present invention will become apparent upon consideration of the following detailed description of the invention when read in conjunction with the drawings, in which:
U.S. Published Application No. 2004/0069648 A1, the entire disclosure of which is incorporated herein by reference, discloses a method for the direct electroplating of a relatively low resistive metal, such as copper, on a resistive substrate. That method allows plating of copper directly on at least one liner layer, where the liner layer(s) act as a diffusion barrier for copper into the dielectric. These diffusion barrier layers typically have a sheet resistance, Rs, which can be several orders of magnitude higher than for currently used copper seed layers. For example, a typical diffusion barrier layer sheet resistance may be in the range of 5 to 300Ω/square, whereas copper seed layers may have a resistance in the range of 1 to 3Ω/square.
The method disclosed in U.S. Published Application No. 2004/0069648 A1 can be described as direct plating or seedless plating. This method is based on the fundamental concept that the driving force for plating, known as the overpotential, η, becomes non-existent or nil at a certain distance from where electrical contact is made, the electrical terminal. For back-end processing of silicon wafers, electrical contact is typically made around the edge of a wafer, using multiple pins or a sealable ring contact. Accordingly, in such processing, as the distance from a wafer edge increases, the overpotential can be expected to decrease. In direct or seedless plating, this overpotential decrease generally occurs to a far greater extent than in conventional plating. This effect is the direct result of the severe potential drop (also known as IR-drop and terminal effect) in the resistive liner.
Even for very thin copper seeds, a plating overpotential exists in the center and edge of the wafer. However, the thinner the copper seed, the greater the expected potential drop from the edge to the center of the wafer. Such potential drop typically results in a strong non-uniform potential or current distribution over the wafer surface, but plating occurs everywhere at the wafer surface, even though at different rates. Many new plating stations have one or more hardware solutions to deal with the terminal effect and provide more uniform current distributions. All of these solutions basically provide different ways to compensate for the high resistance of the thin seed.
The path of the current flow from the electrical contacts with the wafer (cathode) to the opposite electrode (anode) in the plating cell can be represented by a set of electronic components, such as resistors and capacitors.
Vapplied=η+I(Rsubstrate+Rsolution) (2)
The difference in plating overpotential for a spot on the wafer close to the electrical terminal (current path 1 in
One method of counteracting the effect of increased substrate resistance resides in making the solution resistance substantially high so that the change in substrate resistance has little or no effect on the potential drop, thereby allowing the overpotential to be essentially the same from edge to center. This concept forms the basis for one technique for uniform current distribution.
One method of increasing the solution resistance involves lowering its ionic strength or conductivity by using an electroplating bath with low acidity. In this regard, see, H. Deligianni et al. “Model of wafer thickness uniformity in an electroplating tool, Electrochemical Processing in ULSI Fabrication and Semiconductor/Metal Deposition II”, Proceedings of the International Symposium (Electrochemical Society Proceedings Vol. 99-9) 83-95 (1999), the entire disclosure of which is incorporated herein by reference. However, such a method may not be sufficient for very thin copper seeds and, in addition, such a method typically requires hardware modifications. Another method involves artificially increasing the solution resistance by using a plater that comprises a porous resistive element placed between a cathode and an anode. “EREX” from Ebara Corporation, is an example of a device that performs this method.
Other methods involve using segmented anodes to modify the current flow distribution In this regard, see, for example, U.S. Pat. No. 5,156,730 to Bhatt et al., U.S. Pat. No. 6,497,801 to Woodruff et al., U.S. Pat. No. 6,660,137 to Wilson et al., and U.S. Pat. No. 6,773,571 to Mayer et al., the entire disclosures of which are incorporated herein by reference. Even though these methods tend to be more complex, they also rely on the solution resistance where the path of least resistance is determined by the distance from the multiple anodes to different spots on the cathode, as well as the polarization of each anode.
Thieves may also be used to provide increased center to edge uniformity. In this regard, see S. Mehdizadeh et al., “Optimization of Electrodeposit Uniformity by the Use of Auxiliary Electrodes”, J. Electrochem. Soc., Vol. 137, No 1, p. 110-116, (January 1990), the entire disclosure of which is incorporated herein by reference.
In all of the above approaches, different kinds of hardware are used in an attempt to create uniform current distribution by correcting the change in overpotential along the surface. Notably, this approach assumes that the overpotential can be described by a continuous function. However, when the substrate resistance is large enough to cause the overpotential to drop to zero, the description of the overpotential along the wafer surface becomes discontinuous. In such case, correction of the effective series resistive by hardware becomes extremely difficult.
U.S. Published Application No. 2004/0069648 A1 provides a method for direct plating, which can overcome at least one of the challenges discussed above, including the situation where the overpotential along the wafer surface can be described as discontinuous. The method disclosed therein imparts a technique for plating across a wafer, having a thin liner only, from the edge towards the center; i.e the wafer coverage is not instantaneous as with conventional techniques but changes with time. This method applies a current waveform, which accounts for the change in plated copper area and is illustrated schematically in
The present invention relates to an apparatus that can perform the method disclosed in U.S. Published Application No. 2004/0069648 A1. Specifically, the present invention relates to an apparatus for direct plating on resistive liners having an integrated in-situ measuring system to follow the actual progress of a plated front during plating. Feed-back of this information to the power supply allows for more precise control of the current waveform to provide a constant local effective current density during plating of the trench and via features.
The present invention is not limited to any specific type of plating apparatus, and includes, for example, cup and/or fountain platers (“Equinox” from Semitool and “Sabre” from Novellus), thin cell platers (“Slim cell” from AMAT and “EREX” from Ebara) and paddle cells (IBM). In addition, the present invention relates to plater configurations independent of cell volume, anode configurations (such as separated anodes or virtual anodes), diffusers for current distribution (resistive and not resistive), thiefs, flow, rotation, and/or solution chemistry.
The current densities necessary to achieve plating in an apparatus corresponding to the invention are not limited and can cover a very broad range. The current densities may, for example, range from about 10 μA/cm2 to about 2 A/cm2, depending on the application, the plating process, the plated material and the metal ion concentration in the plating bath. The current densities may typically be expected to range from about 0.1 mA/cm2 to about 100 mA/cm2, such as from about 3 mA/cm to about 60 mA/cm2. The voltage depends on the tool configuration. While not limited, the voltage employed typically ranges from about 0 to about 50 volts, such as from about 0 to about 20 volts, or from about 0 to about 10 volts.
The solution chemistry of the plating bath is not limited and includes all plating bath materials disclosed in U.S. Published Application No. 2004/0069648 A1. For example, the plating bath may comprise a copper salt, optionally containing a mineral acid, and optionally one or more additives selected from the group consisting of an inorganic halide salt, an organic sulfur compound with water solubilizing groups, a bath-soluble oxygen-containing compound, a bath-soluble polyether compound, or a bath-soluble organic nitrogen compound that may also contain at least one sulfur atom.
While copper is the primary conductive material contemplated for deposition, an apparatus falling within the scope of the present invention can be used to plate other materials. Examples include all platable metals, alloys, composites, semiconductors and/or polymers from aqueous, non-aqueous or mixed electrolyte solutions or melts. Metals that can be plated according to processes falling within the scope of the present invention may include, for example, those selected from the group consisting of Cu, Ag, Au, Pb, Ni, Pd, Co, Pt, Rh, Ru, Cr, Sb, Bi, Sn, In, Fe, Zn, Cd and and alloys, mixtures, and multilayers of the same. Other metals that may be plated can include, for example, those selected from the group consisting of Re, Tc, Os, Ir, Se, Te, Mn, and alloys, mixtures, and multilayers of the same, as well as alloys, mixtures and multilayers of any of the above metals with Al, Mg, W, V, Ti, Ta, Mo, Ce, Ga, Gd, Hf, Zr, La, Y, Sr, Tl, Eu, Dy, Ho and Nb. In addition, oxides, sulfides, phosfites, and borides, of any of the above metals may be used, as well as any alloys mixtures or multilayers of any of the above materials with Si, C, Ge, As, O, P, S, and/or B.
Metals that may be plated further include elemental semiconductors such as Si and Ge, which may further include C, H and/or F, and alloys, mixtures, and multilayers of the same. In addition, materials that may be plated include: semiconducting oxides, such as ZnO and TiO2; III-V semiconductors such as InAs, InP, InSb and GaS; II-VI semiconductors such as CdSe, CdS, CdTe, ZnS, ZnSe, ZnTe; and tertiary and quaternary semiconductor compounds of combinations above and with Cu, Sr, Ba, and alloys, mixtures, and multilayers of the same. In addition, materials that may be plated include: conducting oxides wherein the metal is selected from the group consisting of Cd, Sn, Ga, In, Cu, Ru, Re, and Pb, and alloys, mixtures, and multilayers of the same; conducting polymers, for example, polypyrrole and polyaniline; semiconducting polymers; and biominerals.
The thickness of the plated metal, while not limited, can typically be expected to range from about 0.02 microns to about 25 microns, such as from about 0.1 microns to about 2 microns, including from about 0.3 microns to about 1 micron.
A plating apparatus falling within the scope of the present invention may be used in the fabrication of semiconductor wafers, such as Si or Ge, with diameters ranging from, for example, about 5 inches (about 120 mm) to about 12 inches (about 300 mm). The apparatus may also be used for substrates with other than circular geometries. In U.S. Published Application No. 2004/0069648 A1, an example was given for a rectangular shaped substrate with electrical contact made on one edge. In such case, the plated front migrates from the edge, where contact was made, towards the opposite edge over time. In such case, in-situ measurement of the copper front position is also desirable.
The liner or diffusion barrier layer or layers on which the conductive metal, such as copper, may be plated is not limited. Examples of materials that can be used include tantalum, tantalum nitride, titanium, titanium nitride, tungsten, tungsten nitride, ruthenium, platinum, rhodium, palladium, rhenium, cobalt, molybdenum, iridium, vanadium, chromium, yttrium, zirconium, niobium, hafnium and mixtures, alloys and multilayers thereof. Further examples include gold, thallium, lead, bismuth, iron, nickel, copper, aluminum, silicon, carbon, germanium, gallium, arsenic, selenium, rubidium, strontium, silver, cadmium, tin, antimony, tellurium, osmium, and mixtures, alloys, and multilayers thereof. The alloys of the above metals can include various alloying materials including, but not limited, to O, S, N, B and P.
A basic configuration of an apparatus relating to the invention is presented schematically in
A representation of an example of a device having an integrated in-situ measuring system to follow the actual progress of a plated front is illustrated schematically in
In devices falling within the scope of the present invention, the in-situ measurement of the plated copper front is not limited to any particular method. Examples of methods that can be used include: potential measurement, optical measurement, AC or impedance measurement, and Eddy current measurement.
Potential Measurement
The potential measurement method is based on the principle that the plating potential will change when the plated copper increases and will reach a certain value when the whole wafer is covered. Measurement of this potential provides an indirect method for controlling the applied current waveform. The potential can be measured between the cathode and anode, for example, as shown in the configuration of
The plating potential (measured potential difference between work piece and reference) is the sum of the electrode potential difference, U, and the IR-drop in the solution (plating potential=U+IR). The electrode potential difference depends on the electrode potential of the reference (see stated values above). A typical range of electrode potential differences, U, for copper plating is about 0.34V to −1V versus NHE; 0.1V to −0.76V versus SCE, or −0.31V to −1.65V versus SMSE. The IR-drop depends on the applied current, solution resistance and the position of the reference electrode in the plating cell. Values may range from 0 to 12V. The IR-drop is the result of the electric field between the anode and cathode, and can be minimized by bringing the reference electrode as close as possible to the substrate surface. In practice, this can be done with a Luggin capillary. A Luggin capillary, is a thin capillary brought close to the work piece (wafer surface in our case), to sample the potential of the working electrode/electrolyte interface without interference of the electric field present between the cathode and anode in the solution.
The electrode potential of a work piece is typically dependent on changes in the chemical composition of the surface (deposition of foreign material or adsorption of organic molecules) and changes in electrolyte composition (e.g. concentration changes due to ion depletion) at the measured interface. Thus, in the case of direct copper plating on a liner, such as ruthenium, by sequential surface coverage according to the teachings of application Ser. No. 10/269,956, the transformation of a bare Ru surface towards a complete Cu surface, with in-between the co-existence of Cu and Ru with changing ratio in surface coverage, is directly measurable by the change in plating potential.
In this regard, see
Since the wafer coverage changes over time, the electric field between the cathode and anode changes over time. The change in electrical field can be measured as changes in the plating potential (through change in the IR-drop) with several reference electrodes positioned at different locations along the wafer radius. Alternatively, at least one fast moving reference electrode along the wafer radius can be used. The plating potential measured by at reference electrodes near copper covered area will be drastically different from those measured near bare liner areas, thus creating a diameter scan or profile of the copper coverage. In one embodiment of this invention, an array of reference electrodes in placed along the wafer radius, and as many volt meters are used to measure the local plating potential. In another embodiment, at least one reference electrode is moving fast over the wafer surface from edge to center, to measure the plating potential profile over time.
In this regard, see
In yet another embodiment, the reference electrode may follow the plated copper front (which is determined by the change-over in plating potential associated with change from liner, such as Ru, to plated metal, such as copper). The position of the reference electrode is a direct measure of the plated copper area.
Optical Measurement
When the reflectivity of the substrate and the plated copper is sufficiently different, light reflection measurements can be used to follow the plated copper front. An application of this principle is schematically represented in
In an actual plating tool, several spots at the wafer may be illuminated through the use of several small light emitting devices (LED's) with the reflectivity monitored with a photo diode array. Alternatively, as for the plating potential method, at least one set of a LED and photo diode can be used, which is scanned rapidly over the wafer surface to measure the reflectivity as a function of wafer radius or track the copper front by positioning itself where the reflectivity difference is the largest (border between bare substrate, such as ruthenium liner, and plated metal, such as copper).
In this regard, see
In another embodiment, the reflectivity of the total substrate area can be measured, with current adjustments made as a function of this measurement. In this case the total measured reflectivity is a linear function of metal coverage and thus plated area, and the current is directly proportional with the measured reflectivity. For example in the case of direct copper plating on Ru, the reflectivity of Cu is higher than the Ru substrate. The maximum change in reflectivity (100%) corresponds to the difference in photo-voltage of a complete Cu surface, Uphoto,Cu, and a complete Ru surface, Uphoto,Ru. The total reflectivity, R(%), of a surface can be defined as:
R(%)=100×[Vphoto,t−(Vphoto,Cu−Vphoto,Ru)]/(Vphoto,Cu−Vphoto,Ru),
with Vphoto,t the photo-voltage measured at time, t. When the reflectivity is proportional to the plated copper area, then the current is directly controlled by the determined reflectivity.
In the case of direct copper plating for back-end of line semiconductor processing, the semiconductor wafer itself can be used as photo-detector (since semiconductors form the bases of photo-diodes). The back of the wafer can be connected to a voltmeter, which is in communication with a computer to control the power supply.
In addition, other optical techniques such as light absorption, light scattering, or light emission (if the structure has light emitting properties) can be similarly used
AC Measurement
Another method of monitoring a plated metal front in an apparatus falling within the scope of the present invention involves AC or impedance measurements by superposition of a small alternating current or voltage to the applied current or voltage for plating by use of a sinusoidal signal generator. Such alternating voltage or current generates a respective alternating current or voltage response determined by the electrochemical impedance of the substrate/electrolyte interface. The electrochemical impedance can be measured using a Lock-in amplifier or Frequency response analyzer (FRA) by comparing the input and output sinusoidal signals which differ in amplitude and phase. The impedance vector (defined by its magnitude, /Z/ and phase angle, φ) can be represented by its real part, Zreal (representing the resistance of the interface) and an imaginary part, Zimag (representing the capacitance of the interface). The measured electrochemical impedance depends strongly on the frequency of the applied sinusoidal signal. At very high frequencies (1 MHz-100 kHz), the series resistance of the system (electrical connections, wires, contact resistance and solution resistance) is measured (typically between 1 to 1000 ohms, depending on tool design and setup). The series resistance contains no information of the substrate/electrolyte interface and is therefore not suitable for this application. At very low frequencies (100 Hz-1 Hz), diffusion processes may determine the measured impedance (known in the art as the Warburg impedance), which is also independent of substrate and therefore not suitable for our application. In the intermediate frequency range (10 kHz-100 Hz), both the capacitance of the substrate/electrolyte double layer (known as the Helmholtz layer in the art, see FIG. 2A), and the resistance associated with the charge transfer over the electrode/electrolyte interface (Rct, as in
The electrochemical impedance for the bare substrate/electrolyte interface will be different than that for the interface of the electrolyte with a plated metal such as copper. Values can, for example, range from about 0.1 ohm cm2 to about 1000 ohm cm2 for the resistance and about 10 μFarad/cm2 to about 100 μFarad/cm2, depending on applied current and potential. Since the impedance depends on the surface area, the total measured impedance will be a function of the plated copper area. As with other methods described elsewhere herein, such measurements can be used in a closed loop to control the current program applied.
In this regard, see
Zreal and Zimag are plotted as a function of plated Cu area in
A flow diagram for a feed-back loop working according to these principles, is shown in the fist part of
An embodiment for controlling the current density during wafer coverage step, using impedance measurement method is shown in
Eddy Current
A somewhat analogous method to the AC measurement method involves the measurement of Eddy currents. Eddy currents are small currents near the surface of a wafer or substrate that exist as the result of an applied alternating magnetic field. Eddy currents are a function of the frequency and the magnetic flux as well as the resistivity and permeability of the surface. Since the surface gradually changes during plating, measured Eddy currents can be used to determine the plated copper area. As with other methods described elsewhere herein, such measurements can be used in a closed loop to control the current program applied. Eddy-current measurement methods are well known in the art of chemical mechanical polishing (CMP) and are typically used for end-point detection. In this regard, see for example, U.S. Pat. No. 6,072,313 to Li, et al. and U.S. Pat. No. 6,707,540 to Lehman, et al., the entire disclosures of which are incorporated herein by reference. In addition, see U.S. Pat. No. 4,556,845 to Strope, et al., the entire disclosure of which is incorporated herein by reference, which describes Eddy-current measurements for in-situ thickness evolution of an electroless deposit (i.e. formed without applied current or voltage).
Each of these methods is based on the measurement by a sensor of a current (Eddy current) induced in the film by an alternating electromagnetic field, and the sensor signal is dependent on the film thickness. Similar approaches can be used for monitoring the plated metal front. Similar to the reference electrode arrays and photodiode arrays used for the potential and optical methods, an array of coils for inducing an alternating magnetic field and Eddy current measurement can be used. Alternatively, a set of coils for Eddy-current measurements can be moved over the diameter of the surface to measure the thickness variation (with respect of before plating) for determination of the plated metal front.
While the present invention has been described in an illustrative manner, it should be understood that the terminology used is intended to be in a nature of words or description rather than of limitation. Furthermore, while the present invention has been described in terms of several illustrative embodiments, it is to be appreciated that those skilled in the art will readily apply these teachings to other possible variations of the inventions.