This disclosure is related to infrared sensing in general and, more particularly, to thermoelectric infrared detectors.
At this point in time, thermal infrared (IR) imaging arrays can't compete with the cryogenically-cooled photon detector arrays in responsivity and detectivity. However, the cryogenic-coolers required for long wavelength photon detectors impose disadvantages such as increased size/cost, and reduced life time. Photon detectors are also sensitive to a limited spectrum of IR radiation. Therefore, there has always been a strong motivation for development of high-performance thermal IR detectors that operate at room temperature. Today, the manufacturing cost of a thermal IR imaging array is still considerably high and the performance is limited by the structure of the detector and more specifically by the heat transfer between the isolated sensitive area and the surroundings.
What is needed is a system and method that addresses the above and related issues.
The invention of the present disclosure as described and claimed herein, in one aspect thereof, comprises a thermoelectric infrared detector. The detector has an absorption platform comprising a material that increases in temperature in response to incident infrared radiation and the platform covering substantially an entire area of the detector. The detector includes a thermocouple substantially suspended from contact with a substrate by at least one arm connected to the substrate.
In some embodiments, the thermocouple comprises a thermoelectric connection embedded in the at least one arm. The absorption platform may connect directly to the at least one arm forming the thermocouple. The absorption platform may also comprise at least one layer dielectric layer with at least two adjacent metal layers. The at least two adjacent layers may be on opposite sides of the dielectric layer and may comprise nichrome. The detector may include an adhesion layer underlying the dielectric layer and the two metal layers.
In some embodiments, the at least one arm comprises Parylene. The at least one arm may be tethered to the substrate by at least one tether, which may comprise Parylene.
The invention of the present embodiment as disclosed and claimed herein, in another aspect thereof, comprises an infrared detector. The detector includes a plurality of support arms proceeding from a substrate and containing a plurality of thermoelectric connections therein. The detector includes an infrared absorber platform in thermal connection with the plurality of arms and heating the arms in response to absorbing infrared radiation. The thermoelectric connections form a thermocouple with the absorber, the absorber acting as a hot junction and the substrate acting as a cold junction, the thermocouple providing a voltage signal on the thermoelectric connections in proportion to the temperature difference between the hot and cold junctions.
In some embodiments, the plurality of support arms comprise Parylene. The detector may further comprise at least one tether tethering at least one of the plurality of support arms to the substrate at a location other than where such support arm joins the substrate.
In some embodiments, the absorber platform covers substantially an entire area of the detector. The absorber platform may comprise a silicon nitride layer with a first nichrome layer on a first side of the silicon nitride layer and a second nichrome layer on a second side of the silicon nitride layer. An adhesion layer may be provided on a lower side of the absorber platform. The detector may include a silicon nitride post interposing the infrared absorber and the plurality of arms.
The invention of the present disclosure as described and claimed herein, in another aspect thereof, comprises a method including providing an infrared absorber, providing a plurality of Parylene support arms supporting the absorber away from the substrate, and attaching a thermally conductive connection from the substrate to the infrared absorber to detect heating of the absorber relative to the substrate. The method may include forming the infrared absorber from a dielectric layer covered on two sides by metal layers. The infrared absorber may be configured to cover substantially all of the support arms.
Infrared (IR) radiation detectors can be categorized into two classes: photon and thermal detectors. The principle of operation in a photon detector is to measure the change in the electrical properties (electronic energy distribution) of a material as a result of interaction between absorbed photons and the electrons. Since thermally generated charge carries will introduce noise in photon detectors, cryogenic cooling is necessary to attain sensitivity to IR wavelength larger than 2-3 μm. In addition, photon detectors will only show sensitivity to a narrow range of IR wavelength based on the engineered band-gap of the material used as the sensing element.
Thermal detectors, on the other hand, operate based on measuring the change in the electrical properties of a material as a result of the temperature change subsequent to the absorption of the IR radiation. With the presumption that the absorption coefficient of the sensing material in a thermal detector is fairly constant for a wide range of IR wavelength, the detector can be used for a wide spectrum and does not require cooling. This is a significant advantage of thermal detectors over their counterparts and has inspired extensive research in universities and industry for decades. Thermal IR detectors are mostly classified in three categories based on the detection mechanism as introduced below.
In resistive detectors, the resistance of a sensing element is changing as the temperature of the element varies corresponding to the amount of absorbed thermal energy. The change in resistance is converted to the change in voltage by passing a constant bias current through the resistance. In these devices the responsivity (defined as the output signal divided by the input radiation power) is proportional to the thermal resistance from the sensing area to the heat sink and the temperature coefficient of resistance.
Pyroelectric detectors operate based on the pyroelectric effect, which is the spontaneous electric polarization as a result of change in the temperature in a pyroelectric film and is measured as a voltage developed on a pair of electrodes covering the two surfaces of the film. Pyroelectric detectors do not respond to constant IR radiation (when there is no temperature change) and radiation modulation (chopping) is necessary for their operation in imaging applications. Similar to resistive detectors, the responsivity in pyroelectric detectors is also proportional to the thermal resistance of the thermally isolated heat collector.
In a thermoelectric detector, the temperature variation in the IR absorption area is turned into a corresponding voltage using a thermopile. The thermoelectric effect is a self-generating transduction mechanism and therefore alleviates the need for a bias signal. As expected, the responsivity in a thermoelectric detector is proportional to the thermal resistance and the difference between the Seebeck coefficients of the two thermoelectric materials used in the thermopile. The rather small Seebeck coefficient of conventional thermoelectric materials can be partially augmented by using a series combination of a number of thermoelectric junctions.
Limits of Detectivity in Thermal Detectors
Noise in thermal detectors originates from both thermal and electrical sources. Random change in the temperature of the sensing element arising from the statistical nature of the heat exchange between the sensor and the surrounding environment is known as temperature fluctuation noise. This noise can fundamentally limit the detectivity of a thermal IR detector. Detectivity in this context is defined as square root of sensing area divided by the noise equivalent power: (D*=AIR1/2/NEP) with the units of cmHz1/2 W−1. With this definition, the temperature fluctuation noise-limited detectivity in a thermal detector is defined as:
where Ab is the absorption coefficient, AIR is the absorption area, Rth is the thermal resistance of the support (assuming that conduction is the dominant heat exchange mechanism), kB is the Boltzmann's constant and T is the system temperature. Interestingly, it is observed that the thermal resistance (Rth) has the same overall effect on the detectivity as it has on responsivity (both improve as the Rth increases). Therefore, the thermal detector (of any kind) exhibit an ultimate detectivity if we assume thermal conduction is removed altogether and the only remaining heat exchange mechanism is radiation. This detectivity is called background fluctuation noise-limited detectivity and is formulated as below:
where σ is the Stefan-Boltzmann constant and the TB and TD are the background and the detector temperature respectively. The detectivity of all thermal devices will always be smaller than this limit. It should be noted that even after greatly suppressing the thermal conduction in a thermal sensing device achieving the background noise-limited detectivity is not guaranteed. This is because other electrical sources of noise such as Johnson noise and 1/f noise (for devices biased at a DC signal) will also affect the detectivity of the IR detector.
Effect of Reducing the Absorption Area
From the size and cost standpoint, scaling down the IR detector pixel size may be desirable. However, from equation 1 it is observed that the temperature fluctuation noise-limited detectivity of a detector is proportional to the square root of AIR. But, the effect of sensing area on the performance is not accurately understood unless the concept of noise equivalent temperature difference (NETD) is introduced. The NETD which is more relevant to the performance of IR imaging arrays is defined as the change in the temperature of an object in the view of the imager which results in a signal to noise ratio of equal one. So the lower this number is the better the quality of the image produced by the imager would be. A general equation defining the temperature fluctuation noise-limited NETD in thermal IR arrays is as follows:
where F is the f/no. of the lens, B is the measurement bandwidth, τ0 is the transmittance of the optics, and (ΔP/ΔT) is the change in power per unit area of the object at temperature T measured within a specific spectral band. The important observation here is that even though NETD is inversely proportional to the IR absorption area (AIR) reducing the pixel size will not necessarily result in smaller signal to noise ratio. The effect of smaller area can be compensated by reducing the f/no. and therefore a lower size/cost IR camera is achieved while preserving the performance.
Employing thermoelectric sensing methods in an IR detector offers many benefits. For example, as mentioned earlier, thermoelectric sensors do not require a bias signal (as opposed to all resistive and some pyroelectric detectors). Therefore, the output signal is free of 1/f noise and Johnson noise is the only source of electrical noise in the sensor. This means that by suppressing the heat conduction of the support structure and carefully designing the resistance of the thermopile (to reduce Johnson noise), the thermoelectric detector is the most likely of all thermal detectors to reach background-noise-limited detectivity discussed above with a very reasonable manufacturing cost.
Resistive detectors and some pyroelectric detectors need a temperature stabilizer in order to operate in a wide range of temperature (e.g. 0-50° C.). The temperature coefficient of resistance in a resistive detector and the dielectric constant in a pyroelectric detector are strong functions of the absolute temperature (the material in use is set at transition temperature to increase responsivity). Therefore, the temperature of the sensing array has to be controlled. This is not the case for a thermoelectric detector in which the reference temperature is always automatically set by the bulk of the substrate which is acting as a heat sink.
Another significant advantage of a thermoelectric detector is the capability to measure constant radiation which eliminates the need for a mechanical chopper.
Collectively, all the above characteristics suggest that a thermoelectric detector is a superior choice for implementation of low-cost, compact and durable IR imaging devices.
Micromachined Thermoelectric IR Arrays
Micromachined thermoelectric IR detectors have received considerably less attention compared to their pyroelectric and resistive counterparts; and majority of current commercially-available IR imaging arrays are based on the two latter types. Considering the aforementioned advantages of the thermoelectric sensing elements, this mediocre popularity among IR imaging producers may be associated with the lower reported responsivity of the thermoelectric IR detectors (˜108 cmHz1/2W−1).
In these devices, the thermoelectric junction is made of doped polysilicon, metals, or a combination of both. In the majority of published work on thermoelectric detectors, the thermally isolated area is either entirely suspended on a thin dielectric (usually silicon nitride) membrane or suspension arms are made of silicon nitride (or silicon oxide). The thermal conductivity of silicon nitride is rather large and therefore the thermal conduction through the suspension arms is increased. Even the thermal conductivity of silicon dioxide is not low enough to provide excellent isolation. Therefore, the overall thermal isolation of the sensing element and consequently responsivity of the detector is usually compromised.
The performance of thermoelectric detectors can be improved by incorporating more efficient thermoelectric material such as Bi—Te compounds. The detectivity for such devices is reported in the range of a 109 cmHz1/2W−1, which is comparable to the detectivity of pyroelectric and resistive devices. However, the present disclosure shows that the detectivity can be improved by an order of magnitude beyond this value with carefully optimizing the detector structure and the thermopile dimension/configuration. This can be achieved without the need for the rare/exotic materials that are typically incompatible with conventional microelectronics fabrication. Thermoelectric IR pixels integrated with low-noise electronic amplifiers can lead to mass-production of low-cost and compact thermoelectric imaging arrays that are suitable for low-power applications (such as space exploration missions).
Advanced Thermoelectric Materials.
The thermal to electrical energy conversion efficiency of a TE device operating between Th and Tc is determined by the average figure of merit (ZT) of the TE material. ZT is a measure of performance of the TE material and depends on combination of three properties of a material: thermal conductivity (x), electrical conductivity (o) and Seebeck coefficient (S):
where T is the average temperature in Kelvin.
One of these techniques is the use of nanostructures that improve or maintain thermoelectric power factor (S2σ) through quantum size effects or interface energy filtering, while their thermal conductivity is reduced through the scattering of phonons at superlattice interfaces. Some examples of these groups are bulk PbTe based materials, BiTe/SbTe superlattices (SL), PbTe/PbSeTe quantum dot superlattices (QDSL), and more recently BiSbTe nanocomposite structure and Si TE nanowires.
TE Properties of Silicon Nanowires
Silicon as a bulk material has a large thermal conductivity (κ>100 W/mK), hence it is a poor TE material (ZT<0.02 at 300K). When it is alloyed with Ge in Si0.8Ge0.2 form, the thermal conductivity reduces to about 5 W/mK and consequently the figure of merit at high temperature is increased (ZT˜1 at 1300K). However, SiGe is still a poor TE material at room temperature (ZT˜0.2 at 300K). Recently, a group of researchers investigated the TE properties of rough Si nanowires (NW). Silicon NWs demonstrated a significantly larger figure of merit even at room temperature (ZT˜1 at 300K). The main reason for this enhancement is believed to be the large reduction in the thermal conductivity (κ˜1.6 W/mK) and enhancement of Seebeck coefficient (S˜240 μV/K) while maintaining a good electrical conductivity (σ˜280 S/cm).
Device Structure
Referring now to
The absorber 102 is made of material with high thermal conductivity, low density, and high IR absorption coefficient (such as silicon nitride) and the thickness of the film is minimized to reduce the heat capacitance. The absorber 102 is connected to a relatively small membrane of silicon nitride 106 via a post 108 in the middle. In the present embodiment, a thermoelectric junction is created by placing polysilicon nanowires 110 in thermal contact with this bottom membrane 106 (e.g., it lays on top of the membrane). The polysilicon nanowires 110 are embedded inside two turning arms 112 that suspend the entire structure and create excellent thermal isolation between the absorber 102 (hot junction) and the bulk of the substrate 104 (cold junction heat sink). In one embodiment, the suspension arms 112 are made of made of Parylene or polyimide.
The thermoelectric nanowires 110 directly convert the temperature difference originated by the absorption of IR radiation to a voltage signal. In order to efficiently suppress parasitic heat transfer, the nanowire thermocouples 110 are embedded in membranes made of organic material with an ultra-low thermal conductivity, such as Parylene or polyimide, to support the suspended mass of the sensing area 102. Some embodiments of the present disclosure are expected to reach the fundamental limit of detectivity (the background fluctuation noise limit at room temperature) currently unattainable by thermal IR detectors.
It should be understood that the number of thermoelectric junctions placed in series is only for illustration, and more or fewer may be present in various embodiments. The arms 112 are turned around the suspended membrane 106 to create a longer path. This lowers thermal conductance while keeping a small total footprint. Thus the pixel size can be reduced resulting in smaller overall package and lower cost. Responsivity and detectivity of a pixel in an IR imaging array may depend on fill factor. In embodiments of the present design, the IR absorber 102 covers the whole area of the array, and almost all the incident IR radiation will be absorbed and converted to image data.
The sensitivity and detectivity of a TE detector increases with the thermal resistance between the hot and cold junctions. The Si NW TE legs 112 of the present disclosure provide a very high thermal resistance for two reasons: first, reduced thermal conductivity of the material while maintaining the TE power factor; and second, very large length to area ratio. The two effects result in a significantly large thermal resistance (>1010 K/W) which is hardly attainable by conventional TE structures.
To take the most advantage of the large thermal resistance of the nanowire TE, one has to carefully design the device structure. The two dominant heat exchange mechanism in such a device are (1) convection through the air and (2) conduction through the support that is embedding the NWs. To eliminate the convection, usually the detector is packaged in a vacuum seal. The heat conduction through the support 112 adds to the total thermal conduction across the two ends of TE junction and results in a smaller responsivity.
Silicon nitride (SiN) has previously been used to form the support 112. However, silicon nitride has a large thermal conductivity (˜30 W/mK) compared to that of Si nanowires (κ˜1.6 W/mK) and therefore, the overall thermal isolation of the structure is deteriorated. For this reason, a support 112 made from Parylene may be used. Parylene demonstrates an extremely small thermal conductivity (κ˜0.08 W/mK) comparable to that of air (κ˜0.03 W/mK). A Parylene membrane significantly reduces the heat conduction path parallel to the Si nanowires 110 resulting in enhanced responsivity and detectivity of the detector 100.
Thermal detectors usually suffer from slower response time compared with the typical photon detectors. The thermal time response of a TE detector can be characterized by:
τ=CthRth (5)
where Cth is the effective thermal capacity that depends on the mass and the specific heat, and Rth is the effective thermal resistance of the device from the IR absorber to the cold end of the sensor. The thermal capacity of the device is attributed to the IR absorber 102, the TE legs 112, and all other supporting materials that are thermally connected to the device. In a device with large fill factor, the large IR absorber dominates the thermal capacity. A smaller IR absorber can enhance the time response; however there is a trade-off between sensitivity of the sensor and the response time. In the present device, both the absorber 102 area/mass and the material of choice are optimized to target a balanced performance. To improve the IR absorption a thin Au-black layer can be coated by low pressure evaporation. The small mass density of Au-black is ˜20 times smaller than Au. This will significantly enhance the time response while maintaining the sensitivity. Au-black layer demonstrates a fairly large IR absorption coefficient (>90%) in the range of λ˜5-17 μm wavelength.
Silicon offers numerous cost and manufacturing advantages when used as a device component but typically is not an obvious choice when it comes to TE properties (ZT of silicon is low as discussed before). However, in the following we will explain why nanowire silicon is an excellent choice for IR sensing applications. In addition to the thermal management of the device, the ultimate responsivity and detectivity of the TE IR detector is dependent on the properties of the TE material. A good TE material is generally one that exhibits the highest figure of merit ZT, where ZT is a measure of thermoelectric performance. However, for a TE IR detector, ZT is not the appropriate parameter for the choice of the TE material. The thermoelectric parameters must enhance the most important sensor performance parameters namely responsivity and detectivity. The responsivity R and the thermal fluctuation noise-limited detectivity DTF of a simple TE detector (no power modulation) is determined by the following two relations:
where N is the number of TE pairs, S is the difference of the Seebeck coefficients of the two legs (i.e. Sp−Sn), Rth is the thermal resistance between the hot and cold junctions, Ab is the IR absorption absorptivity, Ar is the fill factor, AIR is the area of the IR absorber, Rel is the total electrical resistance of the TE legs, T is the absolute temperature, and kB is the Boltzmann constant. If we ignore non-ideal heat conductions and assume that the thermal conduction between the hot and cold junctions is only due to the TE pairs we have:
And for the electrical resistance of the TE leg we have:
where lTE and ATE are the length and the cross section area of each TE leg, respectively. Substituting Rth and Rel in (6) and (7), we have:
Based on equ. (10) in order to achieve a high responsivity, a TE material with large Seebeck to thermal conductivity ratio is desired. This does not necessarily mean a large ZT as generally expected for a superior TE material. For example, if we compare Bi2Te3, PbTe, and Si0.8Ge0.2 as three conventional TE materials, at room temperature Bi2Te3 has the highest ZT˜1, and SiGe has the smallest ZT˜0.2 (n or p at doping concentration˜1019 cm−3). However, SiGe at this doping level has a very large Seebeck coefficient (S˜650 μV/K) as compared with Bi2Te3 (S˜210 μV/K) and PbTe (S˜100 μV/K). This results in a significantly larger S/κ ratios for SiGe. Therefore, a TE IR detector made with SiGe will have a larger responsivity compared to a similar device made from Bi2Te3 or PbTe. For the case of detectivity, ZT/κ is the selection rule. This factor, however, is larger for Bi2Te3.
To demonstrate the performance of a typical TE IR detector versus different TE materials, we calculated the responsivity and detectivity of a TE IR detector with similar device structure when it is made with BiTe, PbTe, or SiGe TE legs. We assumed a device with total absorption area of 30 μm×30 μm, SiN suspended layer under the TE sensors with thickness and width of 100 nm and 350 nm, respectively. We assumed cylindrical TE legs each with a length of 150 mm and calculated the responsivity and detectivity versus the diameter of the TE wires. We further assume similar TE properties both for n and p type materials as listed in Table 1 shows the comparison of the responsivity and detectivity of this device made with different TE materials. Similar values of detectivity for BiTe and responsivity for Si based TE IR detector have already been reported.
As shown in
Thermal Analysis
In the design of the TE IR detector, in addition to the choice of materials used for each element of the device, we have to consider several important geometrical features to optimize the detector performance. Some if these features are: the number of TE couples N, their length l and diameter d, support membrane thickness tm, IR absorber area AIR and thickness tIR. The polysilicon nanowires are fabricated by oxidizing larger polysilicon beams. After oxidation the oxide layer will be removed and the NW is embedded in Parylene. The theoretical model calculations used here are very much similar to that of Vashaee et al. used for modeling of InP thin film coolers. The Si NW parameters are extracted from the experimental data reported by Hochbaum et al. To demonstrate the performance of NW polysilicon TE IR detector we have calculated and compared the responsivity, detectivity, and response time of a design with total absorption area of 30 μm×30 μm, cylindrical TE legs each with a length of 150 μm.
Table 1 lists the parameters used in our calculations.
Responsivity
Once the equivalent thermal resistance across the hot and cold junctions is determined, the responsivity of the detector can be estimated using equ. (6). One way to improve the TE responsivity is to increase the number of nanowires N. However, this will reduce the overall thermal resistance. Therefore, it is important to optimize the number of nanowires versus other parameters of the device. We determined that for our device three pairs of NWs in each beam gives the highest responsivity.
In Table 1 it is seen that smaller wire diameter can result in larger responsivity as expected. We also considered two different membranes one made from SiN and one from Parylene with similar geometries for comparison. It is interesting to notice that for the case of NW, the device with Parylene membrane results in a responsivity that is two orders of magnitude larger. This is mainly due to the extremely small thermal conductivity of Parylene (˜0.08 W/mK) that would significantly reduce the parasitic heat conduction to the substrate.
Detectivity
There exists a trade-off between the responsivity and detectivity in terms of optimizing the geometry of the TE wires. Increasing the ratio of the total length to the cross section area of the wire lNW/ANW would increase the thermal resistance of the wire. That would enhance the responsivity of the detector; however, the detectivity decreases due to the increase in electrical resistance resulted from larger Johnson noise.
In order to achieve reasonably enhanced values for both parameters, we design the device structure to achieve a detectivity close to the theoretical limit of 1.98×1010 cmHz1/2/W, while maximizing the responsivity of the device.
Response Time
There is also a fundamental trade-off between the responsivity of the TE IR detector and its thermal time response as they depend in opposite ways on the thermal resistance of the TE wire. In order to enhance the time response of the proposed device while maintaining its high responsivity, we intend to reduce the heat capacity of the device instead (see equ. 5). For this purpose, we propose to use thin (˜0.5 um) and low density (˜1 g/cm3) black gold deposited on a thin silicon nitride layer for the IR absorber to reduce the thermal mass, hence decreasing the response time. This will reduce the time response of a 50 nm Si NW IR detector below 100 ms, which is appropriate for video frame rate applications. See
Finite Element Analysis
In order to confirm the results of our models we solved the heat transfer equation for the three dimensional structure using finite element method in COMSOL. Heat conduction in all segments and radiation from and to all the surfaces are considered in this analysis. It was observed that for a very small amount of IR radiation (˜1 nW), there exists a detectable temperature difference across the TE legs (˜0.9 C). The TE pair in the sensor is capable of producing measurable voltage for temperature differences in the range of one thousandth of a degree. This simulation agrees with our calculations that show two orders of magnitude enhancement in responsivity (˜106 V/W) compared to that of conventional uncooled IR detectors (i.e. <104 V/W)
Fabrication Process Flow
Referring now to
Next in
A thin layer of polysilicon is deposited, selectively ion implanted and patterned to form the thermoelectric traces 908 as show in
Next, the oxide 910 from the oxidized polysilicon wires 908 is removed in BOE as shown in
It should be noted that in some embodiments, the wires 908 (denoted 110 in the finished product shown in
A thin layer of Parylene 912 is deposited and patterned in oxygen plasma to form the thermally-insulating enclosure for the nanowires 910 in
In
Referring now to
Referring now to
The thermoelectric junctions are formed by sputtering/patterning two different traces 1104, 1106 and then the Parylene film 1108 is deposited in a Parylene-coating chamber at room temperature and is consequently patterned in O2 plasma (
Below is a description of one way in which the steps above were implemented to produce a detector according to the present disclosure.
The fabrication process begins with a single side polished silicon 1101. The wafer is cleaned prior to any deposition to make sure that it is free of any contamination. Any contamination may cause some unknown effects and undesired film formation in the later steps.
There are different choices of sacrificial layers 1102, 1103. Polymers such as photoresist can be used as a sacrificial layer but they are not suitable for high temperature processes since they might burn. Some polymers can tolerate high temperature but ash technique which is used for removal is harmful to Parylene films which itself is a polymer. Other sacrificial layer like silicon dioxide, silicon nitride, polysilicon, etc. can also be used but except silicon dioxide, other materials either hard to remove or their etchant attacks other material on the wafer. Silicon dioxide can be etched in Hydrofluoric solutions (HF). The HF solution slightly attacks Parylene and silicon but this is not the concern here, the important is that it strongly attacks oxide and gives a good selectivity.
After cleaning, sacrificial oxide is deposited. This can be done either in oxidation furnace or PECVD. PECVD oxide is preferable because this film will be removed later on and has higher etch rate in the etchant comparing to the thermal oxide. Also the oxide deposition rate in PECVD (2 um per hour) is much higher than the growth rate in furnace (more than 8 hours for 2 um).
Undoped silicon wafers can be very expensive and doped ones may short the thermoelectric traces to each other and cause malfunction. To avoid this, a thin layer of an insulator material should be deposited. This layer will not be removed and should not be etched in HF solution. Silicon nitride is the choice of option since it can tolerate high temperature, it is slightly attacked in HF, and it can be deposited with the common IC fabrication tools. Another requirement is that the insulator film should have high thermal conductivity to dissipate the transferred heat from the hot element quickly. Silicon nitride has high thermal conductivity and can rapidly conduct any local heat to the other cold areas.
Silicon nitride was chosen for the present build because it could be deposited using PECVD and has high deposition rate. Upon different parameters in the process, the deposited film may have different etch rates. A recipe was developed to produce films with low stress and low etch rate in BOE and is shown in Table 2.
After nitride deposition, the film should be patterned to form a SiN membrane 1104 on the center of the sacrificial oxide which will act as the hot junction.
Thermoelectric wires 1104, 1106 are required to generate voltage due to the temperature difference on their ends. Among metals, Bismuth's Seebeck coefficient is relatively large. It was decided to use sputtering technique instead of thermal evaporation. In general, sputtering provides better sidewall coverage.
One of the thermoelectric wires, was made from polysilicon since it has higher ZT. Polysilicon is deposited in a LPCVD furnace at which should be followed by annealing for dopants activation at. Since this film is deposited at high temperature, lift-off is not an option because photoresists are polymers and they cannot withstand temperatures higher than 150° C. unless they are cured. If they are cured, they can no longer be removed in Acetone and another method which is called ash technique should be used for removal. So, the film has to be dry etched in ICP. Another consideration is that a recipe should be used for etching polysilicon that does not etch the underneath layer especially since polysilicon is thin and timing the process is difficult. This polysilicon layer is deposited over silicon nitride and silicon dioxide. Thus, a great selectivity is required. In addition, the etching should be isotropic and a great undercut can be attained and hence, the width of the wire can be controlled. Thus, a recipe was developed based on SF6 plasma for etching the polysilicon layer. In the developed recipe the etch-rates of photoresist, silicon dioxide and polysilicon are 85, 43, and >1000 nm/min respectively.
The only problem that was observed with this technique was that the widths of the wires on the sidewalls were much smaller than other places. In other words, the polysilicon etch-rate on the sidewalls is more than the flat surfaces. This non-uniform etching can be taken care of by changing the wire patterns. Thus, in the design step, wires with larger widths on the side walls are drawn.
Parylene is deposited at room temperatures with a Specialty Coating Systems (SCS) tool. The thickness of the result film depends on the amount of the loaded dimer. Parylene-C with different thicknesses were deposited and patterned. Oxygen based plasma is used to etch the Parylene film in ICP. Since photoresist is a polymer as well as Parylene, it cannot be used as a mask. Even if the thickness of the photoresist mask is chosen much thicker than the thickness of the Parylene film, the etched film result will not have sharp and good sidewalls. A hard mask such as silicon dioxide should be used.
The next step in the fabrication process is absorber 1110 deposition. Since the absorber 1110 may be deposited at high temperature, higher than 300° C., Parylene C is not proper because its melting point is 290° C. Parylene N has almost the same characteristic but it has higher melting point, 480° C. Thus, Parylene N films were deposited by acquiring the necessary dimer and applying some modifications inside the tool.
The sacrificial layer 1103 for absorber 1110 was deposited next. Again, for the sake of simplicity, photoresist was used as the sacrificial layer and copper was used as the absorber material. As it was shown in
Different recipes for Cu sputtering were tried to avoid heat damage to the sacrificial photoresist. Among different parameters in the process, the applied power to the target had the greatest effect. By reducing this power, a uniform film with no heat damage to the sacrificial layer was deposited. This deposited film should be etched to form the absorber 1110. This can be done by using a photoresist as a mask and wet etching the Cu film.
After patterning the absorber 1110, the absorber and the device can be released by submerging the device in acetone to remove the sacrificial photoresist followed by BOE dip for removing the sacrificial oxide. Devices may be built with different numbers of Parylene arms 112 (
To avoid baking, devices may be released from the backside of the wafer. There are two known ways to etch a wafer from the backside. One way is Bosch process or DRIE (deep reactive ion etching) which results to steep side walls. The other way is anisotropically wet etching with KOH or TMAH. For this process, larger holes on the backside are required. Both of the techniques were pursued to release the devices.
After completing a process on the wafer, the front side was protected with 2 um of PECVD oxide for wet etching the backside. After an hour of etching in TMAH, it was observed that the front side has been attacked and the polysilicon wires were wiped off the front surface. Apparently, PECVD oxide is not a good protecting mask. Another protective layer, Protek, was added to the front side and etching lasted for 6 hours.
When the Parylene film goes under heat cycles, an internal stress will be induced. The author believes that the film eases the internal stress at the annealing temperature and the induced stress is the result of thermal coefficient mismatch between the Parylene film and the underneath layer. It has been shown that at first, the deposited Parylene has tensile stress, but after a heat cycle, the stress will become compressive. Specifically, Parylene N goes under phase change at and which these phase changes will reduce the internal stress. To further lessen this stress, in any heat cycle, the sample should be slowly cooled down. This induced stress is the result of thermal mismatch between the Parylene film and the underneath layer.
Since the generation of stress inside the Parylene film is inevitable, two small supports (of Parylene, for example) may be added to the Parylene film 1108 to hold the arms (112
The absorber 1110 (also 102 of
The absorber deposition comprises 5 steps. First a nitride layer was deposited in PECVD. Then, a thin layer of nichrome should be deposited followed by PECVD nitride again. The last step which is deposited at the top of nitride layer is nichrome deposition using sputtering technique. After this, another Parylene film may be deposited to protect the top films from exposure to HF vapor. However, if the nichrome is thick enough it would protect the underneath layers form HF. Then the absorber 1110 was patterned. The thickness of the photoresist should be carefully chosen since the absorber is composed of different layers and it takes time to etch all of them.
Nichrome can be wet or dry etched. Special photoresist with excellent adhesion to nichrome is required to mask the nichrome layer from its etchant (TFN). Otherwise, the photoresist will peel off or a large undercut occurs. Dry etching is also possible and can be done in chlorine based plasma. The selectivity of nichrome to photoresist in the developed recipe is 24 over 400 which is not good at all. In this work, 5 um thick resist is spun on the wafer and used as the mask.
There were four steps in the formation of the absorber 1110: etching the top nichrome, nitride, nichrome, and finally nitride. After this last step, photoresist can be removed and the devices can be released with either of wet or vapor phase etching techniques.
Referring now to
In some embodiment, an adhesion layer 1910 may underlie all or a portion of the bottom metal layer 1908. The adhesion layer 1910 may comprise a thin layer of silicon nitride. The adhesion layer 1910 may be utilized to enhance adhesion of the platform 902 to the underlying structure to which it is attached.
It will also be appreciated that to maximize sensitivity of the device 1900, thermal resistance between hot and cold junctions should be maximized. Parylene, having a low thermal conductivity, may be used to fabricate various structures of the device 1900, such as the turning arms 112. As described above, following deposition of Parylene, other fabrication steps may be performed. Thus, in some embodiments, Parylene-N may be advantageous over Parylene-C due to its higher melting point. The Parylene polymer may be deposited and then pattern using oxygen based plasma. Following patterning, oxygen plasma should be avoided through the rest of the fabrication. As described above, with respect to
Thus, the present invention is well adapted to carry out the objectives and attain the ends and advantages mentioned above as well as those inherent therein. While presently preferred embodiments have been described for purposes of this disclosure, numerous changes and modifications will be apparent to those of ordinary skill in the art. Such changes and modifications are encompassed within the spirit of this invention as defined by the claims.
This application claims the benefit of U.S. Provisional Application No. 61/422,397 filed Dec. 13, 2010, and PCT Application No. PCT/US2011/064744, filed Dec. 13, 2011, herein incorporated by reference in its entirety for all purposes.
Filing Document | Filing Date | Country | Kind | 371c Date |
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PCT/US2012/041902 | 6/11/2012 | WO | 00 | 6/13/2014 |
Number | Date | Country | |
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61422397 | Dec 2010 | US |