US20080055584A1

US20080055584A1 - Optical transmission filter with extended out-of-band blocking

Info

Publication number: US20080055584A1
Application number: US11/849,026
Authority: US
Inventors: Atul Pradhan; Jay Anzellotti; Joseph Foss; Ligang Wang; Turan Erdogan
Original assignee: Semrock Inc
Current assignee: Semrock Inc
Priority date: 2006-09-01
Filing date: 2007-08-31
Publication date: 2008-03-06
Also published as: US20110216399A1; US8300313B2

Abstract

In accordance with the invention, a filter is fabricated by a modified form of the process disclosed in U.S. Pat. No. 7,068,430. In particular, the method is modified to take into account the effect of absorption by filter material. The method is exemplified by the fabricating of an ultraviolet light transmission filter for transmitting a band within the range 230-320 nanometers. The resulting filter comprises plurality of hard-coating, thin-film layers of alternating high and low index of refraction. The improved filter provides high transmission, sharp edge slopes, and deep and extended out-of-band blocking. As compared with currently available filters, the filter provides transmission up to three or more times greater, edge slopes up to four times sharper, and deep extended out-of-band blocking extending further, even through the visible range.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Ser. No. 60/841,551 filed Sep. 1, 2006 and entitled Optically Transmitting Filters in the Wavelength Region of 230-320 nm., U.S. Provisional application Ser. No. 60/841,552 filed Sep. 1, 2006 and entitled Single-Coating Fluorescence Filter And Three-Coating Filter Set, and U.S. Provisional application Ser. No. 60/875,359 filed Dec. 18, 2006 and entitled Optically Transmitting Filter in Wavelength Region of 230-320 nm with Extended Blocking. The '359, '551 and '552 applications are each incorporated herein by reference.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH

Not Applicable.

FIELD OF THE INVENTION

This invention relates to optical transmission filters and, in particular, to methods of making improved transmission filters and the resulting improved products and improved equipment that they permit. The invention is particularly useful for filters, such as ultraviolet light filters, for which completely transparent filter materials are not available.

BACKGROUND OF THE INVENTION

Optical transmission filters are useful in a wide variety of applications including spectroscopy and fluorescence microscopy. Filters are used in these applications to block unwanted light that would otherwise manifest as spurious light that could swamp the signals to be detected or distort the images to be seen.
Optical transmission filters typically transmit a desired range of wavelengths (referred to as a transmission band) and block wavelengths outside the transmission band (out-of-band wavelengths). Ideally they would transmit all light within a desired band and block all light outside the band. In reality, in-band transmission incurs some attenuation and out-of-band blocking is incomplete. Moreover, the spectral extent of blocking is limited, i.e. blocking may substantially diminish for light of wavelengths not far removed from the transmission band.
Referring to the drawings, FIG. 1A schematically illustrates the spectral transmission of an ideal optical transmission filter. An ideal filter would transmit all light having wavelengths within a band between a low wavelength λL and a high wavelength λH (the Transmission, T, is equal to 1). An ideal filter would block all light outside the band (T=0). λ_Land λ_Hare the wavelengths at which the filter transitions between blocking and transmitting.
Real filters invariably block a small portion of the light to transmitted (T<1) and transmit a small portion of the light to be blocked (T>0). Moreover, the blocking may become less effective for wavelengths spectrally away from the transmission band. These properties are schematically illustrated in FIG. 1B showing the effect of a filter with less than perfect transmission, finite transition regions, less than perfect blocking, and out-of-band transmission. The proportion of light transmitted, the steepness of the transition lines and the extent of the blocking are important parameters in many applications.
Transmission filters are particularly important in optical measurement and analysis systems. Some such systems, e.g. fluorescence systems, use light of one wavelength to excite a sample of material and then measure or view an optical response of the excited sample at another wavelength. The excitation light is delivered to the sample by an excitation light path, and the optical response of the sample is delivered to the eye or measuring instrument by a collection path. Transmission filters between the source and the sample can be used to block spurious light from the excitation path. The steeper the filter transition lines, the more effectively spurious signals are blocked. The lower the transmission loss, the more light from the desired excitation band reaches the sample. Moreover, if the optical response being measured differs considerably in wavelength from the excitation light, the transmission filter needs extended out-of-band blocking to prevent transmission of spurious light that can scatter into the collection path.
UV fluorescence spectroscopy is based on the fact that when some materials are excited by ultraviolet light (light that is composed of wavelengths too short to be visible) they respond by the emission of near-UV and/or visible light (“fluorescent light”). In such apparatus it is important that the UV excitation path not transmit visible light that can also be transmitted as a spurious signal through the collection path.
FIG. 2 is a simplified schematic diagram of a UV probe 20 designed to excite a sample 21 by UV light and to collect visible fluorescent light from the sample. In essence, the probe comprises a UV source 22, an excitation path 23 for transmitting the UV light to the sample 21 and a collection path 24 for transmitting the fluorescent response light from the sample 21 to a detector 25. The excitation path 23 for UV light ideally transmits only UV light that will excite specific materials (“markers”) in the sample. In reality, UV light sources may include or can generate spurious visible light by a number of mechanisms. The spurious visible light can scatter off the sample 21 into the collection path 24 to the detector.
Absorption spectroscopy is another optical analysis technique used in identifying materials and quantifying concentrations. In absorption spectroscopy light of one or more discrete bandwidths is transmitted through a first path and through a sample. Light from the illuminated sample is transmitted through a collection path to a detector that can measure the amount of light the sample absorbed. The amount of absorption provides information regarding the identity of unknown materials or the concentration of known materials. Spurious light through the first path can provide incorrect or inaccurate results.
It should be clear that the steeper the filter slope at the transition wavelengths λ_L, λ_H, the greater the amount of unwanted light that can be filtered out, avoiding spurious results. The greater the in-band transmission of the filter, the greater the input of desired light. And the greater the extent of out-of-band blocking, the less spurious light at the output to interfere with measurement or viewing.
Systems using UV excitation light, particularly UV bands in the wavelength range 230 to 320 nanometers, are particularly useful. The term “bands within the wavelength range” as used herein is intended to include smaller wavelength bands included within the range, e.g. 250-270 nanometers, as well as bands that encompass the range, e.g. 220-325 nanometers. Bands within the 230-320 wavelength range have attained prominence for use in biomedical applications as diverse as drug discovery, genomics and proteomics, immunology, chemical process tracing and threat biodetection. UV bands in this range are highly useful in the fluorescent detection of nucleotides, proteins and enzymatic molecules.
Unfortunately existing filters and equipment leave much to be desired for bands within the 230 to 320 nanometer range. Few commercial filters are available in the range, and none provide the combination of high transmission, steep edge slopes and deep, extended out-of-band blocking needed for high performance detection and measurement.
Typical commercial filters are metal-dielectric filters and soft-coating thin film filters. Metal-dielectric filters provide relatively low transmission: typically only 10-30%. The low-transmission in such filters is inherent because transmission performance is inversely related with achievable blocking.
“Soft-coating” thin-film filters, as well as those that achieve partial blocking using colored absorbing glasses, are not suitable for high intensity light sources in the 230-320 nanometer range. In the UV range, soft-coating materials suffer from severe reliability, durability and spectral stability issues. Even moderate amounts of illumination by high intensity UV sources can cause soft coatings and colored substrates to “burn out”, solarize or photodarken.
A new approach to making highly discriminating optical filters and the resulting improved products are disclosed in U.S. Pat. No. 7,068,430 which is incorporated herein by reference. This approach offers considerable promise for application to filters for the visible range where essentially transparent materials are available. The present invention is an extension and modification of the '430 method to produce advantageous filters for shorter wavelengths where completely transparent materials are not available.

SUMMARY OF THE INVENTION

In accordance with the invention, a filter is fabricated by a modified form of the process disclosed in U.S. Pat. No. 7,068,430. In particular, the method is modified to take into account the absorption of short wavelengths by filter material. The method is exemplified by the fabricating of an ultraviolet light transmission filter for transmitting a band within the range 230-320 nanometers. The resulting filter comprises plurality of hard-coating, thin-film layers of alternating high and low index of refraction. The improved filter provides higher transmission, sharper edge slopes, and deeper and extended out-of-band blocking. As compared with currently available filters, the filter provides transmission up to three or more times greater, edge slopes up to four times sharper, and deep out-of-band blocking extending into and even through the visible range.

BRIEF DESCRIPTION OF THE DRAWINGS

The advantages, nature and various additional features of the invention will appear more fully upon consideration of the illustrative embodiments now to be described in detail in connection with the accompanying drawings. In the drawings:
FIGS. 1A and 1B are schematic illustrations of the spectral transmission of ideal and real optical transmission filter;
FIG. 2 is a simplified schematic diagram of a UV probe to excite and collect optical fluorescence from a sample;
FIG. 3 schematically illustrates an improved optical transmission filter
FIG. 4 is a schematic view of a computer-controlled deposition apparatus useful in making filters;
FIG. 5 is a process flow chart for making the long-wave pass component of a filter;
FIG. 6 is a process flow chart for making the short-wave pass component;
FIG. 7 is a graphical illustration of the theoretical and measured transmission spectra of a exemplary filter;
FIG. 8 illustrates the optical density spectrum of the exemplary filter; and
FIG. 9 is a table giving the index of refraction for HfO2 at wavelengths of interest.
It is to be understood that these drawings are for purposes of illustrating the concepts of the invention and, except for data graphs, are not to scale.

DETAILED DESCRIPTION OF THE INVENTION

Referring to the drawings, FIG. 3 schematically illustrates an improved optical transmission filter. The filter 30 comprises a substrate 31 having one or more surfaces 32 and 33 for supporting thin film hard coatings. The support surfaces 32, 33 are typically opposing optically smooth, planar major surfaces of a thin substrate. The hard coatings forming the transmission filter (e.g. interference filter components 34, 35) can overlie respective surfaces 32, 33 or they can both overlie the same surface. See U.S. Provisional Patent Application 60/841,552 incorporated herein by reference. In the embodiment illustrated a first interference filter component 34 is disposed overlying a first surface 32 and a second interference filter component 35 is disposed overlying the second surface 33. The first filter component 34 comprises alternating layers 34A, 34B of at least two materials of relatively higher refractive index (34A) and relatively lower refractive index (34B), respectively, to form a long wavelength pass filter component that transmits the passband wavelengths but blocks wavelengths below the passband. The second filter component 35 comprises alternating layers 35A, 35B of at least two materials of relatively higher refractive index (35A) and relatively lower refractive index (35B) to form a short wavelength pass filter component that transmits the passband wavelength but blocks wavelengths above the passband. The first and second filter components thus cooperate to transmit light within the passband and to block light outside the passband. One or both of the materials may be materials that absorb small, but not negligible, amounts of light within the passband wavelengths.
In a preferred embodiment, the filter 30 has a passband of ultraviolet light within the range of 230 nanometers to 320 nanometers. The substrate 31 is substantially transparent to ultraviolet light, and the first and second interference filters 34, 35 comprise hard coatings of non-metals that may absorb small amounts of ultraviolet light. Typically, the filters 34, 35 each comprise 30 or more alternating layer pairs. The substrate is advantageously fused silica or calcium fluoride, and the coatings preferably comprise alternating layers of silica and hafnia.
The improved filters described herein are advantageously made by a data processor-controlled deposition system. The preferred deposition system is an ion beam sputtering deposition system using an ion beam assist source for depositing hard coatings combined with an integral optical monitoring system for monitoring deposition. A data processor, responsive to signals from the monitoring system, processes the signals and directs the growth of the layers.
FIG. 4 is a schematic view of an advantageous data processor-controlled deposition apparatus 400 for making the filter by ion beam sputtering disposition with optical monitoring under data processor control. The apparatus 400 comprises a vacuum chamber 401 having an interior accessible by a sealable port 402 such as an o-ring sealed door. The chamber 401 includes a pump port 402 for coupling to one or more evacuating pumps (not shown) such as mechanical and low pressure cryogenic pumps.
Within the chamber 401 is a substrate mount 403 which is advantageously a rotatable spindle mount. Also within the chamber are a plurality of material targets, a deposition ion beam source 404, and a mounted substrate 405. One of the targets 406 is positioned in relation to the ion beam source and the substrate so that an ion beam from the source will sputter material from the target onto the substrate in a substantially uniform layer. Typically there are separate targets for each material to be deposited on the substrate, and the targets are moveable to and from the sputtering position. There are usually two material targets: one for depositing a high optical index material, such as hafnia (HfO2), and the other for depositing a low index material, such as silica (SiO2). The targets are moveable so that deposition can be switched automatically from one material to the other. An Hf metal target can be used during the hafnia deposition and is preferably chosen to have Zr contamination of less than 0.8%.
An assist ion beam source 407 is disposed in the chamber 401 in position to bombard the substrate 405 with an ion beam. Normally during the deposition of any one material, the substrate is simultaneously bombarded by sputtered material and by ions from the assist ion beam source 407. See J. M. E. Harpe et al., “Modification of Thin Film Properties by Ion Bombardment During Deposition,” in Ion Bombardment Modification of Surfaces, Ed. By O. Auciello and R. Kelly, from Beam Modification of Material, Vol. 1 (Elsevier, Amsterdam, 1984).
In the preferred embodiment of this invention using hafnia and silica, the assist ion beam is turned off during the deposition of hafnia (HfO₂) and turned on during the deposition of silica (SiO₂). The use of the assist beam during hafnia (HfO₂) deposition results in films with undesirably high crystallinity, absorption (due to hafnia layers with extinction coefficient >1×10⁻³), and scatter. We have further found that an important factor for reducing the UV extinction in thin films of both hafnia and silica is the regulation of flow of O₂into the deposition chamber. The rate of O₂injection during deposition determines the stoichiometry of the hafnia and silica layers. In particular, the formation of HfO₂in the hafnia layer from Hf metal precursor atoms and O₂molecules has a profound effect on the absorption characteristics of the film. The optimum stoichiometry is achieved with a flow of 12 sccm of O₂of which 6 sccm are from the target O₂, and 6 sccm from the ion source. These flow settings achieve hyperstoichiometric hafnia thin films with reduced UV absorption.
Both the sputter deposition and the assist bombardment can be activated by a deposition control system 408. The control system 408 can start or stop deposition precisely by turning on and off the deposition ion beam source 404 or by removing or engaging a mechanical shutter (not shown) that covers the substrate. Further details concerning ion beam sputtering deposition systems can be found in U.S. Pat. No. 4,142,958 issued to David Wei et al. on Mar. 6, 1979 and U.S. Pat. No. 4,793,908 issued to Gene Scott et al. on Dec. 27, 1988, both of which are incorporated herein by reference. See also Juergen Becker, “Ion Beam Sputtering,” Handbook of Optical Properties, Vol. 1, Thin Films for Optical Coatings, Ed., by R. E. Hummel and K. H. Guenther (CRC Press, Boca Raton, 1995).
The above depositional process produces low absorption hafnia layers. The hafnia (HfO₂) material layers exhibit a small extinction coefficient of <5×10⁻⁴leading to low absorption. This low extinction coefficient correlates with a realized O (Oxygen) to Hafnium (Hf) atomic ratio greater than 2.0 (hyperstoichiometry) in the hafnia layers.
It is believed that the presence of excess oxygen in the hyperstoichiometric hafnia (HfO2) reduces optical absorption by quenching dangling bonds in the amorphous-crystalline hafnia (HfO2) layer mixture. Such hyperstoichiometry (N(O)/N(Hf)=2.16) in hafnia layers is also confirmed by a low oxygen to hydroxide ratio (in this case N(O)/N(OH)=1.37) since a correlation of hyperstoichiometry with a oxygen/hydroxide ratio is reported in a previous E-beam evaporated hafnia thin-film study (Optical and Microstructural Properties of Hafnium Dioxide Thin Films, J. P. Lehan, Y. Mao, B. G. Bovard, and H. A. Macleod, Thin Solid Films, 203 (1991) pp 227-250).
In the advantageous arrangement shown here, a beam splitter 415 picks off a portion 416 of the monitoring light beam 417 from source 409 and detects it with reference detector 412. The signal detector 413 detects the portion 418 of the beam 417 that passes through the coated substrate (or a “witness” substrate) being monitored. Advantageously, the filters 411A and 411B are positioned to ensure that a sufficiently narrow band of wavelengths is monitored.
The filters 411A, 411B can be narrow band interference filters, adjustable diffraction-grating monochromators or combinations thereof. Further details concerning optical monitoring of thin films as they are being deposited can be found in U.S. Pat. No. 6,649,208 issued to Wayne Rodgers on Nov. 18, 2003, which is incorporated herein by reference. See also H. Angus Macleod, Thin Film Optical Filters (3 ^rdEd., Institute of Physics, Bristol, 2001) and H. A. Macleod, “Turning Value Monitoring of Narrow-Band All-Dielectric Thin-Film Optical Filters,” Optica Acta. Vol. 19, pp. 1-28 (1972).
The data processor 414 collects data from the signal and reference detectors 413, 412, implements the mathematics associated with optical monitoring algorithms and instructs the deposition control system 408 when to stop depositing any given thin film layer based on the result of the mathematical calculations prescribed by algorithm.
The manner in which the data processor 414 controls the apparatus 400 via the deposition control system 408 to generate the optical filters according to the present invention will now be described. In particular, the data processor 414 is programmed to instruct the apparatus 400 when to stop depositing each layer of the optical filter being manufactured. The data processor 414 follows two separate processes in determining when a deposition of a layer should terminate depending upon whether a long-wave-pass component or a short-wave-pass component is being manufactured. These two processes will be described in turn.
FIG. 5 illustrates the process flow executed by the data processor 414 when manufacturing a long-wave-pass (“LWP”) filter component. However, prior to initiating the process of FIG. 5, a design for the LWP filter is prepared. In the exemplary embodiment, the LWP filter has N layers (typically N≧30) and comprises at least two materials: a relatively lower-refractive-index material and a relatively higher-refractive-index material. The exemplary initial design for a steep LWP edge filter includes a quarter-wave (“QW”) stack of (0.5H L 0.5H)ˆN where L and H represent layers of high and low index materials with a quarter-wave of optical thickness at the reference wavelength. The reference wavelength is chosen so that the longer-wavelength edge of the QW stopband is close to the desired transition wavelength of the LWP filter component.
Once the initial design is setup, a desired target spectrum is constructed, which typically includes the wavelength ranges of both the blocking and passband regions, as well as the required blocking level and minimum transmission and allowable ripple within the passband. The edge steepness is thus indirectly defined as the wavelength separation between the blocking region and the passband.
The layer thicknesses of the initial design are then optimized against the target spectrum by an optimization routine known in the art. Exemplary optimization routines include the variable-metric or simplex methods implemented in standard commercial thin-film design software packages, such as TFCalc by Software Spectra, Inc., and The Essential Macleod by Thin Film Center Inc. Usually, with the proper choice of the initial design, the optimization quickly converges and the optimized structure is not very different from the initial structure. Special treatments are required for the first layer (toward substrate) and the last layer. The metric thickness of the first layer should be required to meet a minimum thickness threshold, typically 10 nm, in order for robust control by the optical monitoring algorithm. As for the last layer, it sometimes becomes too thin and, consequently, should be eliminated. The structure should be re-optimized whenever there is any modification to the layer thickness.
In preparing the initial design of the long wave pass filter component, it is important to take into consideration the effect of fabrication conditions on the applied layers. The indices of refraction of the applied materials, particularly in UV long wave pass filters, are functions of temperature, pressure and thermal treatment. Here the materials are coated on a substrate typically held at an elevated temperature (roughly 150° C.) in a near vacuum atmosphere. Moreover the deposited materials are, after deposition, typically finished by annealing (baking) them at an elevated temperature for several hours—typically 425° C. for 2-4 hours. The result is that the index after fabrication is different than the index during fabrication. In general, this difference is very small for coatings used in visible light filters and can usually be ignored as negligible. But in UV filters the difference is somewhat larger and should be considered in the initial design, as it affects the optical monitoring process during filter fabrication. Specifically, the coating indices during fabrication should be targeted so that the final indices after deposition, annealing and cooling will be indices desired.
In making the present filters HfO2 is the material most sensitive to fabrication conditions. The correlation at different wavelengths between the index during deposition (“in situ”) and the index at room temperature after annealing is given in the Table set forth as FIG. 9. The indices are specified as complex indices of refraction with the “real part” being the Refractive index and the “imaginary part” being the extinction coefficient. Values for wavelengths not listed may be determined sufficiently accurately by interposition. The variation of the index for SiO2 is not significant for this filter.
In application, the design created uses the after annealing index values. The calculations that are part of the fabrication monitoring process use the “in situ” values so that the end result is in accordance with the design.
With the LWP filter design at hand, the data processor 414 receives design data and deposition rate data as input at 501. The design data describes the designed thin-film structure of the LWP filter with a physical thickness d_iand an index n_ifor each i^thlayer. n₁is either n_L, or n_H, where n_Lis the refractive index of the low-index material and n_His the refractive index of the high-index material. n_Land n_Hare each known as a function of wavelength λ. The deposition rate data describes the known starting deposition rate of the deposition apparatus 400 shown in FIG. 4 for each of the two materials. In the exemplary embodiment, the deposition rate data is within about +/−5% of the actual deposition rate and is in units of Å/sec. The starting rate estimates for each of the two materials are referred to as r_Land r_H, and hence each layer will have a starting rate estimate r_idepending on whether it is made of low-index or high-index material.
At 502, the transmission T_i, as a function of physical thickness d for each/h layer is calculated at a series of wavelengths in the transmissive band of the finished filter. Consequently, the calculations at 502 result in a series of curves T_ivs. d at each of the series of wavelengths in the transmissive band of the finished filter. Such calculations are performed using standard mathematical methods for calculating the optical properties of thin-film filters. See, for example, H. A. Macleod, Thin-film Optical Filters, 3^rdedition (Institute of Physics, Bristol, 2001).
Advantageously, instead of calculating each T. vs. d curve at one corresponding wavelength in the series of wavelengths, each T. vs. d curve is calculated by averaging a plurality of T_ivs. d curves calculated at a range of wavelengths surrounding the corresponding wavelength. For instance, assume that the series of wavelengths includes 241 nm and 242 nm. Instead of calculating a T_ivs. d curve at just 241 nm, this T_ivs. d curve is advantageously calculated by averaging T_ivs. d curves calculated at, for instance, 240 nm, 241 nm, and 242 nm. Further, the T_ivs. d curve at 242 nm is advantageously calculated by averaging T_ivs. d curves calculated at, for instance, 241 nm, 242 nm, and 243 nm. One skilled in the art will appreciate that invention is not limited to this averaging procedure and the range of wavelengths used.
At 503, an optical monitoring wavelength λ_mis selected from the series of wavelengths in the transmissive band of the finished filter, thereby identifying a single curve T_ivs. d at λ_m, from the series of curves computed at 502. The monitoring wavelength λ_m, is determined based on the contrast of the monitoring signal within each layer. The contrast is defined as the relative range of the monitoring signal within the layer of interest. The higher the contrast, the more robust the process flow of FIG. 5 will be with respect to random signal noise.
Advantageously, the relative separation between the monitoring and cutoff wavelengths should be at least about 2%. Once above 2%, the monitoring wavelength λ_mshould be chosen to maximize the contrast of each layer. In addition, the optical thickness of the first layer toward the substrate has a significant impact on the signal contrast for the rest of the coating. Therefore, the optical thickness of the first layer should be close to three quarter-wavelengths at the monitoring wavelength λ_m.
Having determined the monitoring wavelength λ_m, at 503, processing advances to 504 where it is determined how the deposition duration for each layer will be calculated. For layers that are predicted to have little error between the designed thickness d and a simulated actual thickness, deposition duration is controlled by optically monitoring transmission levels T_mthrough the layer during deposition. For the other layers, their deposition durations are controlled using an expected deposition time t_ibased upon designed (“theoretical”) thickness d_iand deposition rate r_i. Accordingly, at 504, the data processor 414 determines which layers are to be optically monitored and which layers are to be timed using an expected deposition time.
To determine which layers will be optically monitored, the data processor 414 enters a simulation mode to simulate deposition of each of the layers of the optical filter. Only the layers 25 that are determined by the simulation to have the least amount of error are selected for optical monitoring. The simulation mode is nearly identical to the process described below with reference to 505 to 522, except that layers are not actually deposited at 505 and 506, the processing described at 508 is skipped, and instead of actually measuring transmission data T_mvs. t at 511, it is generated. T_mvs. t is generated by adding random noise to the theoretical data T_ivs. d at λ_mfrom 502 and 503. In the exemplary embodiment, 0.2% peak-to-peak random noise is used, and the maximum amount of error (“threshold”) to select a layer for optical monitoring is to have no more than about 0.2% error from the theoretical thickness d_i. The error calculation, in this regard, is discussed in more detail below with reference to 518 and 519. The layers that are simulated to exceed the threshold amount of error are flagged to have their deposition duration controlled by the best estimate of the deposition rate r_ifor that layer or from an average of the rates of the previous layers of like material (typically 10 to 20 of such layers).
After determining which layers are to be optically monitored at 504, actual deposition of the layers of the LWP filter begins at 505. In particular, the substrate is loaded into the deposition apparatus 400 of FIG. 4, the apparatus is pumped down to a vacuum, and deposition of the first layer (current layer i) is initiated at 506. The expected deposition time t_ifor layer i is calculated as the desired thickness d_idivided by the estimated deposition rate r_ifor the layer or from an average of the rates of the previous layers of like material at 507. It should be noted, however, that calculation of the expected deposition time t_iat 507 may be calculated prior to beginning actual deposition of the current layer i at 506.
After calculating the expected deposition time t, it is determined whether the current layer i has been identified as a layer to be optically monitored for controlled deposition duration. If the current layer has not been so identified, deposition of the current layer terminates when the expected deposition time t_ifrom 507 expires, as shown at 509. After the expected deposition time t_ihas expired, processing advances to 521 where the next layer is queued up for deposition, as shown at 510.
If it is determined at 508 that the current layer i is to be optically monitored, the actual transmission T_m, is measured at 511 as a function of actual time transpired t until about 95% of the expected deposition time t_ihas elapsed. Once about 95% of t_ihas elapsed, a new deposition duration is calculated at 512-520. In particular, at 512, 513, and 514, using the T_ivs. d at λ_mcurve from 502 and 503, a two-dimensional (2D) array of additional curves is generated by plotting the values of T_iagainst a 2D array of time vectors t_jk. In particular, at 513, transmission T_ijis generated by plotting T_iagainst the values t_j=d/r_jwhere r_jrepresents, for each j, a deposition rate having a value close to the predicted value r_i. That is, the set of all r_jvalues is a range of values surrounding the predicted value r_i. Accordingly, j is an index that counts the number of r values that come from the range surrounding the predicted value r_i. At 514, for each value of j, transmission T_ijkis generated by plotting T_ijagainst the values t_jk=t_j+Δt_k, where Δt_krepresents various values used for a uniform time shift.
At 515, it is determined whether there is more than one extremum in the curve T_ivs. d at λ_m. If there is more than one extremum at 515, then each of the 2D array of curves generated at 512-514, is scaled in two ways at 516. First, the mid-point between the two extrema for each T_ijkcurve is scaled by a factor so that it equals the mid-point between the two extrema of the measured data T_mvs. t. Second, the maximum and minimum values on each T_ijkcurve are scaled by scaling uniformly about their mean so that the difference between the maximum and minimum for each curve T_ijkis the same as that on the measured curve T_mvs. t. If there is one or no extremum at 515, then the mean of each T_ijkcurve is scaled at 517 by a uniform factor so that it is equal to the mean of the measured curve T_mvs. t.
After scaling at 516 or 517, processing advances to 518 where error is calculated. For each of the 2D array of generated T_ijkcurves, the root-mean-square (RMS) error between each T_ijkcurve and the measured curve T_mvs. t is computed. Typically this computation is performed only for data between about 10% and 95% of the expected deposition time t_i. Afterwards, the values of j and k that yield a minimum RMS error at 518 are identified at 519. Therefore, the curve T_ijkvs. t_jkis taken to be the best approximation of the actual curve T_mvs. t for layer i. At 520, the curve T_ijkvs. t_jkis compared against the design curve T_ivs. d at λ_mfrom 502 and 503, and the time t_jkat which the layer should be terminated is computed. When the measured time t reaches t_jk, the deposition for the optically monitored layer i is terminated.
After deposition of the current layer i has completed, the apparatus 400 of FIG. 4 is reconfigured at 521 to start depositing the material associated with layer i+1, and the process loops back to 506. However, if all layers of the filter have been deposited, the LWP filter is complete, and processing stops at 522.
FIG. 6 describes the process flow executed by the data processor 414 when manufacturing a short-wave-pass (“SWP”) filter component. The process illustrated with FIG. 6 is based on the inventor's observation that the inverse of the monitoring trace (i.e., the transmission of the monitoring light as a function of time) within each layer follows a sinusoidal pattern. As will be shown, four parameters, β₁, β₂, β₃, and θ_m+1are needed to fully describe the behavior of the monitoring trace for each layer in the absence of appreciable absorption, whereas a fifth parameter, D, must be included when such absorption is present, as is true for the UV filters of the present invention.
Assume initially that at the monitoring wavelength the incident medium, deposited materials, and substrate are all lossless (practically true in many, but not all, cases). At normal incidence, each layer may be described by its characteristic matrix: $\begin{matrix} [\begin{matrix} \cos θ & - ⅈ \sin θ / n \\ - ⅈ n \sin θ & \cos θ \end{matrix}] & (1) \end{matrix}$
where n is the refractive index of the layer, θ is the accumulated phase within the layer, and i in equations 1 through 8 (and only in these equations) is the square root of —1, or i=√{square root over (−1)}. (It should be noted that although this specification is described in the context of light striking a filter at normal incidence, one skilled in the art will appreciate that this invention also applies to polarized light striking a filter at non-normal incidence.) θ is expressed as: $\begin{matrix} θ = \frac{2 π}{λ_{m}} nd & (2) \end{matrix}$
where d is the metric thickness of the layer and λ_mis the monitoring wavelength. Assuming an assembly of m layers have already been deposited, the transmission of the monitoring light within the (m+1)^stlayer, the present layer, may be expressed as: $\begin{matrix} T = \frac{4 n_{a} n_{s}}{H} & (3) \end{matrix}$
where T is the level of monitoring signal within the present layer (transmission), and n_aand n_sare the refractive indices of the incident medium and substrate, respectively. H is defined as:
H=β ₁+β²cos(2θ_m+1)+β₃sin(2θ_m+1) (4)
β₁, β₂, and β₃, are defined as: $\begin{matrix} β_{1} = \frac{n_{a}^{2} + n_{m + 1}^{2}}{2} ({\langle p \rangle}^{2} + \frac{{\langle q \rangle}^{2}}{n_{m + 1}^{2}}) + 2 n_{a} Re ({pq}^{*}) & (5) \end{matrix}$
where Re(pq*) is the Real Part of the product of the complex number p and the complex conjugate of the complex number q. p and q are defined in equation (8) below. $\begin{matrix} β_{2} = \frac{n_{a}^{2} - n_{m + 1}^{2}}{2} ({\langle p \rangle}^{2} - \frac{{\langle q \rangle}^{2}}{n_{m + 1}^{2}}) & (6) \\ β_{3} = (\frac{n_{a}^{2}}{n_{m + 1}} - n_{m + 1}) Im (p^{*} q) & (7) \end{matrix}$
Im(pq*) is the Imaginary Part of the product of the complex conjugate of the number p and the complex number q. p and q are defined as: $\begin{matrix} [\begin{matrix} p \\ q \end{matrix}] = \prod_{l = 1}^{m} [\begin{matrix} \cos θ_{l} & - ⅈ \sin θ_{l} / n_{l} \\ - ⅈ n_{l} \sin θ_{l} & \cos θ_{l} \end{matrix}] [\begin{matrix} 1 \\ n_{S} \end{matrix}] & (8) \end{matrix}$
where θ_Iis accumulated phase in the I_thlayer.
For monitoring wavelengths in the UV between 220 and 320 nm, the incident medium (vacuum or air) can be assumed to be lossless but the deposited materials for the thin-film layers and substrate exhibit absorption with losses due to a non-zero extinction coefficients in imaginary parts of their respective refractive indices. For this reason, the in-situ optical monitoring algorithm is advantageously modified with an envelope slope factor to model the in-situ degradation of transmission monitoring signal (T) vs. optical thickness as well as the modification of the algorithmic fitting parameters to include calculated effects of substrate absorption and material absorption of the depositing film layers and the previously deposited back-side thin-film stack.
Specifically, the right hand expression in Equation (4) is modified to be:
H=[β′ ₁+β′₂cos(2θ_m+1)+β′₃sin(2θ_m+1)]/[1+Dθ _m+1] (9)
where D is an additional in-situ fitted parameter used to model the decrease in transmission due to extinction in the UV for the in-situ depositing layers (taken to be front-side thin-film stack without loss of generality), substrate, and, if applicable, the previously deposited back-side thin film stack.
Further β′₁, β′₂, and β′₃are given by $\begin{matrix} β_{1}^{'} = [β_{1} δ + {(1 - α)}^{2} \frac{R_{bR}}{T_{b}}] / (1 - α) & (10) \\ β_{2}^{'} = β_{2} \frac{δ}{1 - α} & (11) \\ β_{3}^{'} = β_{3} \frac{δ}{1 - α} & (12) \end{matrix}$
Here β₁, β₂, and β₃are defined as in equations 5, 6, and 7, and the constant $\begin{matrix} δ = γ + (2 α - α^{2}) \frac{(1 - A_{fR}) R_{bR}}{T_{b}} & (13) \end{matrix}$
Where T_bis the transmittance through the previously deposited back-side thin film stack, R_bRis the substrate to back-side reflectance, A_fRis the absorption of the front side stack, and α is the substrate single-pass absorption. The constant γ is given by: $\begin{matrix} γ = 1 + \frac{A_{fR} R_{bR} + A_{bR}}{T_{b}} & (14) \end{matrix}$ where A_bRis the back-side thin film stack absorption.
Based on the above equations, the relationship between the monitoring trace T and the accumulated phase θ_m+1within the present layer is established. The inverse of the monitoring trace is sinusoidal, as demonstrated by the expression for H. Further, only five parameters, β₁, β₂, β₃, θ_m+1, and D are needed to fully describe the behavior of the monitoring trace in the present layer. Because the thickness d=r×t, where r is the deposition rate and t is the deposition time, a relationship between T and r or t is also established. If the deposition rate is constant, the accumulated phase θ_m+1is proportional to the deposition rate. Therefore, during the deposition process, the deposition rate may be retrieved with high accuracy by fitting the in-situ measurement of the monitoring trace to the five parameters.
With this groundwork, the process of FIG. 6 will now be described in greater detail. However, prior to initiating the process of FIG. 6, a design for the SWP filter component is prepared. The process of designing a SWP edge filter is very similar to that of the LWP filter, with several exceptions. First, the initial structure is (0.5 L H 0.5 L)ˆN. Second, the shorter wavelength edge of the QW stopband should be aligned with the desired cutoff wavelength. Third, if the first layer next to the substrate is a low index layer, it should be removed.
With the design of the SWP filter at hand, the design data, as well as deposition rate data are received as input at 601. The input data has the content and format described with reference to 501 in FIG. 5. At 602, the transmission curves T_ivs. d at a series of wavelengths for each I^thlayer are calculated as described with reference to 502 in FIG. 5. Choosing the best monitoring wavelength λ_mat 603 is similar to that described with reference to 503 in FIG. 5, except that it may be more advantageous to select π_mby taking an average of a series of wavelengths than it is for an LWP filter.
At 604, the p parameters are calculated for each layer at wavelength λ_musing equations (1) through (8) described above. At 605, a determination is made as to which layers should have their deposition duration controlled by optical monitoring and which layers should have their deposition duration timed using an expected deposition time t_i. Such determination is made by simulating the deposition of each layer and selecting the layers having the least amount of simulated error to be optically monitored. Deposition of the other layers will be timed using the expected deposition time t_i.
The simulation process occurs by executing the processes of 606 to 617 as described below. However, actual deposition does not occur at 606 and 607, the processing described at 609 is skipped, and instead of measuring T_mvs. t at 612, it is generated. T_mvs. t is generated by adding random noise to the theoretical data T_ivs. d at λ_mfrom 602 and 603. In the exemplary embodiment, 0.2% peak-to-peak random noise is used, and the maximum amount of error (“threshold”) to select a layer for optical monitoring is to have no more than about 0.5% error from the theoretical resulting thickness d_i. The error calculation, in this regard, is described in more detail below with reference to 613. The layers that are simulated to exceed the threshold amount of error are flagged to have their deposition duration controlled by the best estimate of the deposition rate r_ifor that layer or from an average of the rates of the previous layers of like material (typically 10 to 20 such layers).
Having determined which layers are to be optically monitored at 605, deposition begins at 606. In particular, a substrate is loaded into the deposition apparatus 400, the apparatus 400 is pumped down to vacuum, and deposition of the first layer (current layer i) is initiated at 607. At 608, the expected deposition time t_ifor layer i is calculated as the desired thickness d_idivided by the estimated deposition rate for the layer r_ior from an average of the rates of the previous layers of like material. It should be noted, however, that calculation of the expected deposition time t_iat 608 may be calculated prior to beginning actual deposition of the current layer i at 607.
At 609 it is determined whether the current layer i was identified as an optically monitored layer at 605. If not, deposition occurs until the expected deposition time t_iexpires, and the deposition apparatus is configured for deposition of the next layer, as shown at 610, 611, and 616. If it is determined that the current layer i is an optically monitored layer at 609, the transmission T_mof the current layer is measured at 612 as a function of actual time t transpired, thereby producing a measured curve T_mvs. t, until about 95% of time t_ihas elapsed. Once about 95% of the time t_ihas elapsed, a new layer time is calculated at 613 to 615.
To elaborate, at 613, T_ivs. t (where t=d/r and T. vs. d at λ_mwas calculated and selected at 602 and 603, respectively) is fit to the measured curve T_mvs. (from 612. The T. vs. t curve is fit to the measured curve T_mvs. t by using a function that minimizes the error between the two curves by varying β₁, β₂, β₃, and the deposition rate r. An example of such a function is the Levenberg-Marquardt method implemented under the name “mrqmin( )” in the book Numerical Recipes in C: The Art of Scientific Computing, by Press, W. H.; Teukolsky, S. A.; Vetterling, W. T.; and Flannery, B. P., 2nd ed., Cambridge University Press, Cambridge, 1995. These calculations result in a calculated deposition rate for the current layer i, or r_ci.
Because of noise in the overall system and the sensitivity of the high-performance SWP filters to small layer-thickness errors, the calculated rates r_citend to be insufficiently accurate if used directly. Therefore, a “best rate” for each layer, r_bi, is calculated at 614 as the average of the calculated rate r_ciand calculated rates r_cj, r_c,j+2, . . . , r_{c,i−4, r} _c,i−2for a certain number (i−j)/2 of previous layers of the same material. In other words, the best rate is a rolling average of the current and previous rates from layers of like material within a certain window. Typically, this window includes about 20 layers.
At 615, the best rate r_biis used to calculate the layer termination time t_t=d/r_bi, and the layer is terminated when the clock reaches this time. Once deposition of the current layer is complete, the deposition apparatus 400 of FIG. 4 is reconfigured at 616 to start depositing the material associated with the next layer i+1, and the process loops back to 607. However, if all layers have been deposited, manufacturing of the SWP filter is complete, and the process ends at 617.
The improved filters have the general structure schematically illustrated in FIG. 3 but are made by the processes described herein in connection with FIGS. 5 and 6. In essence, the filters comprise a transparent substrate advantageously having a pair of optically flat planar major surfaces and a plurality of alternating layers of relatively high index and relatively low index materials. The materials are hard oxide coating materials such as SiO₂, Ta₂O₅, Nb₂O₅, HfO₂, TiO₂, and Al₂O₅.
The filters differ from filters described in the '430 patent in that the effect of absorption is accounted for in the design and fabrication. They differ from pre-430 patent conventional filters primarily in the number of layers (more than 30 and typically more than 100) and in that the thicknesses of layers deposited are controlled by the processes of FIGS. 5 and 6 to produce a highly sloped steep edge (edge steepness may be as low as about 0.8% or lower). The edge steepness, in this regard, is measured by dividing (a) the edge width from the 50% transmission wavelength to the optical density 6 (“OD6”) wavelength by (b) the 50% transmission wavelength. Accordingly, lower steepness values indicate greater slope. Optical density (“OD”) is a measure of the blockage encountered by impinging light and is defined as follows:
OD=−log₁₀(T) (15)
where T is the transmittance having a value between zero and one. OD6 therefore corresponds to a transmittance of 10₋₆. Advantageously the edge steepness, as defined above, may be less than about 0.58% at 266 nm and 0.78% at 248 nm. However, the edge steepness may be increased if necessary.
In addition, the filters so made exhibit an average transmission well above 40% within the operating range of the passband between 230 and 320 nm. Average transmission of the filters typically exceeds 90% in the operating range greater than 320 nm. The filters thus provide performance exceeding that of the highest performing conventional soft-coating filters with a more robust and durable hard-coated structure.
The invention can now be more clearly understood by consideration of the following example: a UV band transmission filter with extended out-of-band blocking was made employing the design and fabrication process described above. The filter was designed to transmit a band of wavelengths within the range of 230 to 320 nanometers and to provide extended blocking. The substrate was a fused silica plate of thickness 2 mm having a pair of optically smooth planar major surfaces. The LWP and SWP filter components were formed on the respective major surfaces. The filter components comprised stacks of silica and hafnia layers of substantially quarter wave thickness deposited as described herein. To reduce UV absorption the flow of O₂was controlled during deposition of both silica and hafnia and the assist ion beam used during the deposition of silica was turned off during the deposition of hafnia. The deposition algorithms were modified as described herein to account for the absorption of UV light by the hafnia layers. The thicknesses in the exemplary filters are set forth in Appendix A. The layers are counted from the substrate outward toward air.
FIG. 7 shows the measured and theoretical transmission spectra of the resulting filter. Curve 1 is the measured spectrum, and curve 2 is the theoretical spectrum.
FIG. 8 illustrates the optical density (OD) spectrum of the resulting filter. Curve 1 is the measured spectrum, and curve 2 is the theoretical spectrum. The OD is a measure of the blockage encountered by impinging light. As previously noted, the out-of-band blocking for this UV band transmission filter extends through the visible spectrum. For all wavelengths in the range 230 to 600 nanometers, the filter provides an average optical density of 3 or more. Indeed, the exemplary filter provides an average optical density of 3 or more for the range 230 to 840 nanometers. Here average optical density (called OD_avg) is defined as ${OD}_{avg} = \frac{1}{λ_{2} - λ_{1}} \int_{λ_{1}}^{λ_{2}} Min [- \log_{10} (T (λ)), 6] ⅆ λ,$
Where Min[a,b] is mathematical notation to indicate that the smaller of the values a and b is to be chosen. The filter also provides an optical density of the average transmission over the wavelength range 320 to 700 nm of greater than 4. Here the optical density of the average transmission (called OD(T_avg)) is defined as $OD (T_{avg}) = - \log_{10} [\frac{1}{λ_{2} - λ_{1}} \int_{λ_{1}}^{λ_{2}} T (λ) ⅆ λ] .$
The resulting exemplary filter is believed to have characteristics superior to any currently available commercial UV fluorescence filter. It provides transmission up to three or more times greater, edge slopes up to four times sharper, and deep extended out-of-band blocking into and even through the visible range.
Because of the superior characteristics of the filter, superior optical analysis systems can be built. Such a system, as described above, would include a source of excitation light for exciting a sample, a filter in accordance with the invention between the source and the sample and a collection light path from the sample.
While we have exemplified our method and resulting filter as a transmission filter having coatings to produce a low pass filter and a high pass filter on opposing surfaces of a substrate, it should be clear that the same method can be used to fabricate a transmission filter where both coatings (low pass and high pass) are stacked on the same surface of the substrate. The method can also be used to fabricate a transmission filter on one surface of the substrate by hard coatings that form a multi-cavity Fabry-Perot transmission filter. If the coatings are stacked on one surface, the opposing surface can be coated for anti-reflection or to extend blocking of out-of-band wavelengths.
It now can be seen that in one aspect the invention is an optical bandpass filter for transmitting a passband of ultraviolet light. The filter comprises a substrate having one or more surfaces for supporting thin film coatings, a plurality of alternating layers of at least two hard-coating materials of higher refractive index and lower refractive index overlying at least one of the surfaces to form a transmission filter. The passband of the filter is a band of ultraviolet light within the range of 230 nanometers to 320 nanometers, i.e. the transmission band of the filter falls within, encompasses or partially overlaps the 230 to 320 nanometer range. The filter has an average transmission of light over the passband exceeding 40% and an average optical density of at least 3.0 at all wavelengths over the range 230 to 600 nanometers and preferrably at least 3.0 over the range 230 to 840 nanometers.
The bandpass filter can comprise a long wave pass filter component and a short wave pass filter component that overlie respective opposing surfaces of the substrate. Alternatively, the long wave pass filter component and the short wave pass filter component can overlie the same surface of the substrate. Or the bandpass filter can comprise a plurality of alternating layers on at least one surface of the substrate forming a multi-cavity Fabry-Perot transmission filter.
In another aspect, the invention comprises an improved optical analysis system comprising a source of excitation light for exciting a sample, an excitation filter between the source and the sample, and a collection light path from the sample. In the improved system, the light source comprises an ultraviolet light source and the excitation filter comprises a filter as described herein.
Yet another aspect of the invention is an improved method of making an optical bandpass filter for transmitting a band of light with extended out of band blocking. The method comprises the steps of providing a substrate having one or more surfaces and forming on one or more surfaces a transmission filter comprising alternating layers of at least two hard coating materials of higher refractive index and lower refractive index. Each of the layers are deposited by a data processor controlled process comprising calculating with the data processor a theoretical transmission T_iof light through the layer, calculating with the data processor an expected deposition time t_iof the layer, measuring during the deposition of the layer for a period of time less then t_ia measured transmission T_mof light through the layer and determining with the data processor when deposition of the layer is to terminate based upon the theoretical transmission T_iand the measured transmission T_m. In the improved process, the calculations of t_iant T accounts for absorption by the relation of Equations (9) thru (14) herein.

It is to be understood that the exemplary embodiment is merely illustrative of the present invention and that many variations can be devised by those skilled in the art without departing from the spirit and scope of the invention.

APPENDIX A


Side 1	Side 2
Thickness (μm): 12.325733	Thickness (μm): 1.758378
Total Layers: 180	Total Layers: 57

Layer	Material	Thickness (nm)	Layer	Material	Thickness (nm)

1	HfO2	72.1007	1	HfO2	27.3195
2	SiO2	118.3490	2	SiO2	20.9656
3	HfO2	85.1500	3	HfO2	22.7797
4	SiO2	114.9216	4	SiO2	37.6872
5	HfO2	82.6366	5	HfO2	26.9187
6	SiO2	111.4661	6	SiO2	38.6993
7	HfO2	107.4115	7	HfO2	25.5595
8	SiO2	92.7005	8	SiO2	34.1848
9	HfO2	102.6364	9	HfO2	24.3603
10	SiO2	107.2082	10	SiO2	35.6352
11	HfO2	87.1395	11	HfO2	26.2768
12	SiO2	109.5288	12	SiO2	38.7735
13	HfO2	91.4296	13	HfO2	26.7182
14	SiO2	108.1881	14	SiO2	38.1082
15	HfO2	81.8771	15	HfO2	25.7298
16	SiO2	110.1988	16	SiO2	35.8083
17	HfO2	73.9249	17	HfO2	25.0468
18	SiO2	117.1318	18	SiO2	36.5451
19	HfO2	74.6909	19	HfO2	26.1482
20	SiO2	118.2505	20	SiO2	38.6671
21	HfO2	75.5438	21	HfO2	26.5937
22	SiO2	106.8061	22	SiO2	38.4960
23	HfO2	75.5688	23	HfO2	25.7947
24	SiO2	106.3660	24	SiO2	36.6766
25	HfO2	84.5039	25	HfO2	25.0609
26	SiO2	113.9206	26	SiO2	36.6864
27	HfO2	76.9341	27	HfO2	25.8315
28	SiO2	119.1098	28	SiO2	38.4870
29	HfO2	70.5075	29	HfO2	26.5693
30	SiO2	110.1970	30	SiO2	38.7309
31	HfO2	76.0482	31	HfO2	26.0688
32	SiO2	108.5060	32	SiO2	36.9925
33	HfO2	80.8123	33	HfO2	25.1015
34	SiO2	102.4766	34	SiO2	36.4162
35	HfO2	73.8582	35	HfO2	25.5644
36	SiO2	107.6290	36	SiO2	38.1222
37	HfO2	77.0410	37	HfO2	26.4967
38	SiO2	111.8720	38	SiO2	39.0124
39	HfO2	67.2644	39	HfO2	26.3862
40	SiO2	94.9101	40	SiO2	37.2234
41	HfO2	64.9878	41	HfO2	25.1252
42	SiO2	76.8883	42	SiO2	35.3620
43	HfO2	63.6517	43	HfO2	25.3871
44	SiO2	110.4563	44	SiO2	37.5519
45	HfO2	70.0142	45	HfO2	26.7525
46	SiO2	98.3208	46	SiO2	38.9845
47	HfO2	75.2259	47	HfO2	26.8832
48	SiO2	100.9608	48	SiO2	36.7390
49	HfO2	75.2577	49	HfO2	24.5900
50	SiO2	93.0265	50	SiO2	32.9317
51	HfO2	72.0313	51	HfO2	24.9154
52	SiO2	91.0647	52	SiO2	37.9697
53	HfO2	56.1579	53	HfO2	27.2033
54	SiO2	98.8476	54	SiO2	40.1149
55	HfO2	74.9020	55	HfO2	26.3818
56	SiO2	85.5257	56	SiO2	27.7252
57	HfO2	59.0061	57	HfO2	15.5180
58	SiO2	102.8053
59	HfO2	63.8348
60	SiO2	90.2354
61	HfO2	57.3333
62	SiO2	86.6766
63	HfO2	56.2852
64	SiO2	89.4719
65	HfO2	58.6218
66	SiO2	88.1946
67	HfO2	68.0857
68	SiO2	102.4020
69	HfO2	61.6486
70	SiO2	86.9727
71	HfO2	71.2438
72	SiO2	87.7043
73	HfO2	55.1169
74	SiO2	90.3453
75	HfO2	57.3322
76	SiO2	85.4162
77	HfO2	55.4564
78	SiO2	71.5981
79	HfO2	53.0274
80	SiO2	77.9571
81	HfO2	59.7391
82	SiO2	86.5060
83	HfO2	60.0115
84	SiO2	76.9315
85	HfO2	52.7560
86	SiO2	79.5779
87	HfO2	62.3061
88	SiO2	82.4643
89	HfO2	55.0188
90	SiO2	79.5853
91	HfO2	50.8281
92	SiO2	71.1860
93	HfO2	52.4135
94	SiO2	79.9608
95	HfO2	51.1334
96	SiO2	67.5792
97	HfO2	60.0648
98	SiO2	87.6077
99	HfO2	50.3849
100	SiO2	70.2799
101	HfO2	51.7803
102	SiO2	68.2664
103	HfO2	46.5611
104	SiO2	68.7605
105	HfO2	50.3361
106	SiO2	73.0590
107	HfO2	45.5139
108	SiO2	66.9389
109	HfO2	46.2534
110	SiO2	68.3094
111	HfO2	52.4229
112	SiO2	52.8991
113	HfO2	44.6834
114	SiO2	64.3372
115	HfO2	41.1402
116	SiO2	67.6132
117	HfO2	54.5554
118	SiO2	65.1206
119	HfO2	43.6465
120	SiO2	63.8078
121	HfO2	44.4390
122	SiO2	72.6333
123	HfO2	54.8816
124	SiO2	55.8602
125	HfO2	40.4550
126	SiO2	61.4907
127	HfO2	40.8874
128	SiO2	57.4055
129	HfO2	45.5921
130	SiO2	79.7559
131	HfO2	43.2964
132	SiO2	61.4557
133	HfO2	43.0496
134	SiO2	51.1259
135	HfO2	45.2922
136	SiO2	25.3388
137	HfO2	50.4883
138	SiO2	57.5332
139	HfO2	44.8209
140	SiO2	81.9174
141	HfO2	46.3080
142	SiO2	61.7248
143	HfO2	39.0360
144	SiO2	52.2586
145	HfO2	36.5175
146	SiO2	58.2430
147	HfO2	39.0385
148	SiO2	49.9179
149	HfO2	36.9217
150	SiO2	56.2932
151	HfO2	35.2279
152	SiO2	50.5663
153	HfO2	39.8732
154	SiO2	58.7650
155	HfO2	35.0772
156	SiO2	49.2266
157	HfO2	37.7815
158	SiO2	56.7485
159	HfO2	35.9983
160	SiO2	53.0305
161	HfO2	37.1014
162	SiO2	56.5459
163	HfO2	37.8429
164	SiO2	54.5702
165	HfO2	34.9456
166	SiO2	49.8230
167	HfO2	38.1749
168	SiO2	59.7611
169	HfO2	44.5530
170	SiO2	29.2983
171	HfO2	42.7338
172	SiO2	52.9270
173	HfO2	36.7455
174	SiO2	55.2726
175	HfO2	40.7526
176	SiO2	57.6055
177	HfO2	35.6880
178	SiO2	51.7944
179	HfO2	44.2760
180	SiO2	115.8012

Claims

1. An optical bandpass filter for transmitting a passband of ultraviolet light comprising:

a substrate having one or more surfaces for supporting thin film coatings;

a plurality of alternating layers of at least two hard-coating materials of higher refractive index and lower refractive index overlying at least one of the surfaces to form a transmission filter wherein;

the passband of the filter is a band of ultraviolet light within the range of 230 nanometers to 320 nanometers, with an average transmission of light over the passband exceeding 40% and an average optical density at all wavelengths over the range 230 to 600 nanometers of at least 3.0.

2. The bandpass filter of claim 1 wherein the alternating layers form a long wave pass interference filter component and a short wave pass interference filter component.

3. The bandpass filter of claim 1 wherein the long wave pass filter component and the short wave pass filter component overlie opposing surfaces of the substrate.

4. The bandpass filter of claim 1 wherein the long wave pass filter component and the short wave pass filter component overlie the same surface of the substrate.

5. The bandpass filter of claim 1 wherein the plurality of alternating layers on at least one surface forms a multi-cavity Fabry-Perot transmission filter.

6. The bandpass filter of claim 1 wherein the optical density of the average transmission at all wavelengths over the range 320 to 700 nm is at least 4.0.

7. The bandpass filter of claim 2 wherein the long wave pass interference filter component comprises alternating layers of silica and hafnia.

8. The bandpass filter of claim 2 wherein the short wave pass interference filter component comprises alternating layers of silica and hafnia.

9. The bandpass filter of claim 2 wherein the interference filters are composed of hafnia (HfO2) material layers exhibiting a stoichiometric ratio of atomic oxygen to atomic hafnium given as N(O)/N(Hf)>2.

10. The bandpass filter of claim 2 wherein the interference filters are composed of hafnia (HfO2) material layers exhibiting a stoichiometric ratio of atomic oxygen to hydroxide (OH) as N(O)/N(OH)<1.6.

11. In an optical analysis system comprising a source of excitation light for exciting a sample, an excitation filter between the source and the sample, and a collection light path from the sample;

the improvement wherein the light source comprises an ultraviolet light source and the excitation filter comprises a filter according to claim 1.

12. A method of making an optical bandpass filter for transmitting a band of light with extended out-of-band blocking comprising:

providing a substrate having one or more surfaces;

forming on one or more of the surfaces a transmission filter each comprising alternating layers of at least two hard coating materials of higher refractive index and lower refractive index;

each of the layers deposited by a data processor controlled process comprising:

calculating with the data processor, a theoretical transmission T_iof light through the layer,

calculating with the data processor an expected deposition time t_iof the layer,

measuring during the deposition of the layer for a period of time less than t_ia measured transmission T_mof light through the layer,

determining with the data processor when deposition of the layer is to terminate based upon the theoretical transmission T_iand the measured transmission T_m; and

wherein the calculation of t_iand T_iaccounts for absorption by the layer by the relation of Equations (9) thru (14) herein.

13. The method of claim 12 wherein the alternating layers form a long wave pass filter component and a short wave pass filter component.

14. The method of claim 12 wherein the alternating layers form a multi-cavity Fabry-Perot filter.

15. The method of claim 12 wherein the at least two deposited materials include silica and hafnia.

16. The method of claim 13 wherein the silica and hafnia are deposited by sputtering.

17. The method of claim 15 wherein the silica is deposited by ion beam assisted sputtering and the hafnia is deposited by sputtering without ion beam assistance.

18. The method of claim 15 wherein the sputtering is conducted in an O₂ambient with the flow of O₂chosen to reduce UV light absorption by the deposited layers.

19. An optical bandpass filter for transmitting a passband of light comprising:

a substrate having one or more surfaces for supporting thin film coatings;

a first interference filter overlying one of the surfaces of the substrate comprising alternating layers of at least two materials of higher refractive index and lower refractive index to form a bandpass characteristic;

a second interference filter overlying one of the surfaces of the substrate comprising alternating layers of at least two materials of higher refractive index and lower refractive index to form blocking in addition to that provided by the first bandpass characteristic interference filter;

wherein:

the passband of the filter is a band of ultraviolet light within the range of 230 nanometers to 320 nanometers, with an average transmission of light over the passband exceeding 40%;

the average optical density at all wavelengths over the range 230 to 840 nm is at least 3.0;

the substrate is substantially transparent to ultraviolet light;

the first and second interference filters comprise hard coatings and non-metals that are substantially transparent to ultraviolet light and cooperate to substantially block light with wavelengths outside the passband over a range that includes visible wavelengths.