I'm releasing a version of CalcZAF that has a new window (see Xray | Calculate Spectrometer Position menu in CalcZAF) for calculating spectrometer positions for both JEOL and Cameca instruments as seen here:
(https://smf.probesoftware.com/oldpics/i61.tinypic.com/2rzqpuv.jpg)
To improve this calculation I'd like to:
1. Get suggestions of other spectrometer geometries (different Rowland circles) to implement...
2. I think we should "crowd source" an effort to refine the refractive index values for the light element spectrometer crystals such as PC1 and LDE1 to improve the accuracy of KLM markers on our spectrometer scanning plots.
So here are the crystals that I would like to hear from those that have tried John Fournelle's technique to "back out" the refractive index values for various multi-layer crystals. See the attachment in this link for more info (remember you have to be logged in as a member to see attachments!):
http://smf.probesoftware.com/index.php?topic=197.msg1732#msg1732
LDE45 and PC0 (nominal 45 angstrom 2d)
LDE1 and PC1 (nominal 60 angstrom 2d)
LDE2 and PC2 (nominal 100 angstrom 2d)
LDEB and PC25 (nominal 150 angstrom 2d)
LDEC and PC3 (nominal 200 angstrom 2d)
Please post your own refractive index determinations from your lab...
John F., please feel free to start!
Below I've attached the default CalcZAF crystal table where you can see various efforts to "adjust" the refractive index values for various light element crystals. This file can be copied into your existing Probe for EPMA folder (assuming you haven't made any changes to your original file CRYSTALS.DAT !). New installations will get this CRYSTALS.DAT file automatically.
I might try to get some value on our vintage JEOL-8600 with LDEC, LDEB and LDE1 crystals, but meanwhile, here are some values I randomly found on the web or in the literature (not even sure if I can find back the exact source of the data...):
Crystal (2d) = Refractive index "k"
PC0 (45 Å) = 0.006
LDE45 (45 Å) = 0.01
PC1 (60.6 Å) = 0.00832
LDE1 (60 Å) = 0.01
LDE1H (62.5 Å) = 0.008
PC2 (95 Å) = 0.021
LDE2 (98 Å) = 0.01
ODPb (100.7 Å) = 0.0175
PC25 (147.66 Å) = 0.02
LDEB (145 Å) = 0.01
PC3 (200.5 Å) = 0.02
LDE3 (200 Å) = 0.02
LDEC (200 Å) = 0.04
Julien
Quote from: Julien on November 21, 2014, 08:08:51 PM
I might try to get some value on our vintage JEOL-8600 with LDEC, LDEB and LDE1 crystals, but meanwhile, here are some values I randomly found on the web or in the literature (not even sure if I can find back the exact source of the data...):
Crystal (2d) = Refractive index "k"
PC0 (45 Å) = 0.006
LDE45 (45 Å) = 0.01
PC1 (60.6 Å) = 0.00832
LDE1 (60 Å) = 0.01
LDE1H (62.5 Å) = 0.008
PC2 (95 Å) = 0.021
LDE2 (98 Å) = 0.01
ODPb (100.7 Å) = 0.0175
PC25 (147.66 Å) = 0.02
LDEB (145 Å) = 0.01
PC3 (200.5 Å) = 0.02
LDE3 (200 Å) = 0.02
LDEC (200 Å) = 0.04
Hi Julien
This is useful. Let the testing begin!
By the way, I checked John Fournelle's early calculations and I'm confused. Did the graph labels for F ka and P ka III get swapped or did I screw up the calculation...?
The point is, John Fournelle made this graph some some time ago, and he showed that depending on the value of the PC0 refractive index, the P Ka 3rd order line will show up on one side *or* the other side of the F Ka line (and hence the corresponding spectral interference position!). But the F ka line in my calculation shows the larger change compared to P ka 3rd order for different refractive index values.
(https://smf.probesoftware.com/oldpics/i59.tinypic.com/316vtrm.jpg)
Anyway, is the refractive index of a PC0 (45 angstrom 2d) really 0.02? According to John F.'s measurements, the answer is yes.
Here is the calculation from the new CalcZAF window:
Spectro position for f ka on PC0 (160 mm), is 41542 (with refractive index correction, k= 0.02)
Spectro position for p ka (III) on PC0 (160 mm), is 41145 (with refractive index correction, k= 0.02)
The point is that with a large enough refractive index (0.02), the P Ka 3rd order line will shift relative to the F Ka 1st order line, enough to fall on the other side of the F Ka position! E.g.,
Spectro position for f ka on PC0 (160 mm), is 41542 (with refractive index correction, k= 0.02)
Spectro position for p ka (III) on PC0 (160 mm), is 41145 (with refractive index correction, k= 0.02)
Spectro position for f ka on PC0 (160 mm), is 41122 (with refractive index correction, k= 0.01)
Spectro position for p ka (III) on PC0 (160 mm), is 41099 (with refractive index correction, k= 0.01)
Spectro position for f ka on PC0 (160 mm), is 40711 (with refractive index correction, k= 0)
Spectro position for p ka (III) on PC0 (160 mm), is 41053 (with refractive index correction, k= 0)
A little help please!
Edit by John: Ok, as Julien has confirmed in the next post, John Fournelle's plot labels in the graph above are reversed.
I agree with John D., I think the label for P Ka (n=3) and F Ka (n=1) in John F. graphic have been inverted. The opposite should be observed. I have recompute the same calculation, and here is the result:
(https://smf.probesoftware.com/oldpics/i58.tinypic.com/am2quv.jpg)
Attached is the XL spreadsheet I used for this calculation. It also contains the list of element / standard / X-ray line / order that John F. suggest to use for these tests (see his PPT under the link posted by John D: http://smf.probesoftware.com/index.php?topic=197.msg1732#msg1732 (http://smf.probesoftware.com/index.php?topic=197.msg1732#msg1732)). Hopefully this will help each of us to determine the refractive index for our crystals.
Aside of this, I wonder... Assuming that the monochromator for a specific microprobe of a same "batch" (e.g., all SX-100 or all JEOL-8200) have been made at the same factory, shouldn't we assume a very similar refractive index? And actually, assuming that the refractive index is depending on the material used, shouldn't we expect the exact same refractive index (or very close) for the same monochromator type? In other word: what are the parameters that control this refractive index?
- The quality of the monochromator (can vary depending on the manufacturer of the monochromator)?
- The material used in the monochromator?
- The exact monochromator spacing (seems that k increase with 2d)?
Julien
Quote from: Julien on November 22, 2014, 09:55:24 AM
- The quality of the monochromator (can vary depending on the manufacturer of the monochromator)?
- The material used in the monochromator?
- The exact monochromator spacing (seems that k increase with 2d)?
Thanks Julien.
The basic problem as John F. and I have surmised is that the manufacturers calculate the 2d spacing *without* accounting for the refractive index of the materials in the multi-layers. The typical material used in the manufacturing of the multi-layers is quite high Z (e.g., W/Si), compared to say LiF and that is why the refractive index is so high for these "crystals".
So when the purchased multi-layer crystal is reported as 59 angstroms 2d, that is *not* (so far as we have seen) accounting for the refractive index.
John Fournelle's class exercise:
http://smf.probesoftware.com/index.php?topic=197.msg1732#msg1732
is to utilize multiple order lines to determine both the actual 2d and the effective refractive index for these multi-layer crystals.
Yes, John, I totally acknowledge John F exercise, indeed the attached spreadsheet should help any user to calculate this optimum k (and 2d) to yield the correct sin-theta. The game, if I understand correctly, is to change the k (and 2d) to match the calculated and the measured sin-theta position of some key peaks. In the spreadsheet, the first sheet contains the list of lambda positions for the element and X-ray line and line order suggested by John F exercise.
If I have time, maybe I'll work on a macro to automatically calculate the optimum k and 2d, using a double-iterative loop to minimize the difference between the theoretical and calculated sin-theta peak position. However, this might be tricky...
Anyway, aside of this, on a mathematical point of view, one can calculate the difference in sin(theta) between the "classical" Braggs law and the revised Braggs law that include the refractive index. This difference (sin(theta) from "classical" MINUS sin(theta) from "revised") can be expressed as follows:
Delta(sin-theta) = k * n * (lambda) / (2d * (n^2 - k))
So when n increases, for the same value of k, the difference of sin-theta should be LESS: assuming delta(sin-theta) is proportional to k*n/(n^2 - k), with (n^2 - k) > k*n, since k is always < 1).
Do you or John F have already some data (peak position of one or more element(s) with different diffraction order on the same monochromator) so I could "play" with it (i.e., trying to build this XL macro to calculate an optimum 2d and k)?
J.
Ok, new version of CalcZAF (v. 10.5.3) allows us to "play" with the refractive index to see the effect on spectrometer position.
(https://smf.probesoftware.com/oldpics/i61.tinypic.com/j0lhfr.jpg)
Edit by John: using this dialog one can calculate nominal spectrometer positions for JEOL (L-value) and Cameca (sin theta) with or with the Bragg refractive index effect.
BTW, do you have an option in CalcZAF for the 100 mm Rowland circle on JEOL (H-type spectrometer)? I'm surprised Paul would not have asked you that already, as it seems he is a great fan of these spectrometers that can give up to 6x more counts than a regular spectrometer with small area crystals...
J.
Quote from: Julien on November 22, 2014, 12:14:31 PM
BTW, do you have an option in CalcZAF for the 100 mm Rowland circle on JEOL (H-type spectrometer)? I'm surprised Paul would not have asked you that already, as it seems he is a great fan of these spectrometers that can give up to 6x more counts than a regular spectrometer with small area crystals...
Yes, with some tradeoff in spectral resolution.
This suggestion is exactly what I am looking for. See point #1 in this post:
http://smf.probesoftware.com/index.php?topic=375.msg1971#msg1971
So 100mm Rowland for JEOL. Any others I should add?
Here is a small macro file that should (hopefully?) ease the determination of the optimum k and 2d. This macro use the "solver" of microsoft Excel, and you will need to activate it (see the PDF help document for instructions on how to activate the Microsoft Excel Solver). I've tested this on my mac (Office 2011) and on Windows 7 (Office 2013). Both worked fine.
All you need are peak position measured on a specific spectrometer / monochromator. A list of recommended element / X-ray line to use for this test is given in this spreadsheet (based on suggestions from John Fournelle).
The spreadsheet determines the difference between the measured and calculated (theoretical) peak position using the Braggs law and the refractive index (k). The solver (macro) is then used to yield an average of peak position differences of zero and to minimize the standard deviation of these differences.
Let me know if this works!
Julien
Yes, please add Cameca 180 mm spectrometers.
Thanks!
Alright, after a few hours of WDS scan on grand'ma JEOL-8600 (26 years old!), I got some results on the 2d-k evaluation on my available multilayers. Results on LDE1 (60 Å) are pretty consistant, independent on the X-ray line / order I choose for the regression. However, I cannot tell this for the other two large-2d spectro I have (LDEC ~100Å and LDEB ~150Å). Here it is (details in the spreadsheet):
- LDE1 (60 Å): 2d = 61.3 Å / k = 0.013
- LDEC (100 Å): 2d = 102.5 Å / k = 0.028
- LDEB (150 Å): 2d = 149.2 Å / k = 0.035
Now, if I exclude some "badly defined (high order) peaks"...
- LDE1 (60 Å): 2d = 61.3 Å / k = 0.014
- LDEC (100 Å): 2d = 102.8 / k = 0.031
- LDEB (150 Å): 2d = 150.0 / k = 0.041
Note that these values are NOT corrected for possibly dynamic (mechanical) shift... I cannot easily verify this (suggestions are welcome for this matter...), although if I assume a shift similar to the other crystals available (PET and TAP for spectrometer with LDEC and LDEB, TAP for spectrometer with LDE1), then here are the results:
- LDE1 (60 Å): 2d = 61.4 Å / k = 0.013
- LDEC (100 Å): 2d = 102.7 Å / k = 0.028
- LDEB (150 Å): 2d = 149.4 Å / k = 0.035
("of course" this shift chiefly affects the 2d of the crystal, not so much the k...)
See the XL spreadsheets for the results (one is a modified copy of the XL macro I wrote - see my former comment, the other are the acquisition results [peak positions]; these results are NOT corrected for possible dynamic shift, which are in the order of 0.1-0.2 mm on my JEOL-8600). I got these results using a high-beam current (most of them 200 nA, some 100 nA), with 2 to 4 seconds counting time (longer on high-order lines), and with a step of 0.1 mm or 0.00035 sin-theta (some 0.25 mm = 0.00090 sin-theta). These could have been refined using a smaller step size and longer counting time, but I did not have enough time to do this today... Also, keep in mind that ALL my monochromators are "normal" area monochromator... Hence the difficulty to get good precision on X-ray line above 3rd-4th order... Even on pure metals for L-lines...
@John Fournelle: maybe, can you suggest the conditions you've used for your WDS scan?
And for comparison, here are the data that John Fournelle mention in his PowerPoint (slide 19):
- PC0 (45 Å): old = 44 Å, 0.01483 => NEW: 44 Å, 0.01
- PC1 (60 Å): old = 61 Å, 0.01 => NEW: 62.1 Å, 0.02
- PC2 (100 Å): old = 95.2 Å, 0.013 => NEW: 98.5 Å, 0.033
- PC3 (200 Å): old = 200 Å, 0.01 => NEW: 204 Å, 0.04
Comments and additional data from other labs are more than welcome!
Julien
Quote from: Philipp Poeml on November 24, 2014, 01:55:49 AM
Yes, please add Cameca 180 mm spectrometers.
Of course since Cameca spectrometers read out directly in sin-theta units, the spectrometer positions for the 160 and 180 mm FC spectrometers are the same.
In fact even JEOL has the 100mm spectrometer positions read out as though they were a 140mm Rowland circle spectrometer (according to Paul Carpenter JEOL seems to be handling the difference in the spectrometer micro-code)- because of course they should be different in L-unit values!). Anyway, I added them to the list to make that clear as seen here:
(https://smf.probesoftware.com/oldpics/i57.tinypic.com/2s1wu2d.jpg)
Here is the output for all 4 options for Fe ka:
Spectro position for fe ka on LIF (140 mm), is 134.7153 (without refractive index correction)
Spectro position for fe ka on LIF (160 mm), is 48113 (without refractive index correction)
Spectro position for fe ka on LIF (140 mm), is 134.7153 (without refractive index correction) <- should say 100mm but it's as though it was a 140mm!
Spectro position for fe ka on LIF (180 mm), is 48113 (without refractive index correction) <- should say 180mm but it's as though it was a 160mm!
I've recently measured the d-spacings for the 3 LDE crystals on our 8530F in an attempt to have PfE display the KLM markers on Plot!ted wavescans much closer to the real peak positions on our probe. I've updated and saved the probe.ini file. Yesterday I created a brand new MDB file (after updating the ini file) on the presumption that the updated d-spacings would be used in the new mdb. Errr, yes AND no!!!
I've attached a screen dump from the log window.....
Why are the CRY2D values correctly updated for F on LDE1, B on LDEB, N on both LDE1 and LDE2 (I didn't change the TAP d), BUT BOTH d spacings for O on LDE1 and LDE2 using the 'old' (inappropriate, default/book) values??
Got me beat this one!!!
In addition to updating the d-spacings in the ini file, I also changed a few of the default settings, e.g. the Magnification (analytical), Magnification (default) and Magnification (Imaging) BUT these haven't been updated either!!
PS: Karsten, I found out why our system wasn't using the last unknown's settings for wavescans.... The UseLastUnknownAsWavescanSetup flag in the ini file was set to 0. I also updated that in the .ini, but that hasn't been implemented either.
SO, I've updated and saved the .ini file (in Notepad++). What else do I HAVE to do to get PfE to use this new updated .ini file??
(somewhat frustrated by PfE NOT using the new info...)
Quote from: David Steele on November 25, 2014, 06:50:27 PM
SO, I've updated and saved the .ini file (in Notepad++). What else do I HAVE to do to get PfE to use this new updated .ini file??
(somewhat frustrated by PfE NOT using the new info...)
Hi David,
Glad to see you getting into the software... but the reason is because it is a scientific "no-no" to change parameters for existing data!
Create a new run and the new values will be used.
john
PS I think you mean you edited the CRYSTALS.DAT file, not the probewin.ini file...
Hi John,
Thanks for the info and corrections.... Yes (sorry) updated the Crystals.dat file, BUT I also updated the probe.ini file re the UseLastUnknownAsWavescansetup, and other (magnification) defaults.
The log window I snipped was in theory a brand new mdb. However because I didn't want to reinvent the wheel yet again (having done that repeatedly over the past 5 months since our initial PfE install) I did the first unk setup in Acquire then immediately did a Load File Setup from an MDB that contained the same light elements as shown. Is this (i.e. using existing data imported via the Load File Setup) why my new MDB isn't using the updated ini and crystals info??
If yes, it seems I really have to start (again) from scratch and not import anything into ANY new MDBs to have the updated config (ini/dat) file information used. Can you confirm (yay/nay)?
Cheers,
David
Quote from: David Steele on November 25, 2014, 07:37:05 PM
Hi John,
Thanks for the info and corrections.... Yes (sorry) updated the Crystals.dat file, BUT I also updated the probe.ini file re the UseLastUnknownAsWavescansetup, and other (magnification) defaults.
OK, but (again) you mean the Probewin.ini file!
Sorry to be so pedantic, but as a programmer I know what a single stray character can do! Much less three!
Quote from: David Steele on November 25, 2014, 07:37:05 PM
The log window I snipped was in theory a brand new mdb. However because I didn't want to reinvent the wheel yet again (having done that repeatedly over the past 5 months since our initial PfE install) I did the first unk setup in Acquire then immediately did a Load File Setup from an MDB that contained the same light elements as shown. Is this (i.e. using existing data imported via the Load File Setup) why my new MDB isn't using the updated ini and crystals info??
If yes, it seems I really have to start (again) from scratch and not import anything into ANY new MDBs to have the updated config (ini/dat) file information used. Can you confirm (yay/nay)?
If you load the file setup from another MDB file into a new MDB file, guess what you get? ;D
Yay!
john
PS One other route is to export the element setups from the sample to the element database (SETUP.MDB) using this button:
(https://smf.probesoftware.com/oldpics/i61.tinypic.com/95n7v5.jpg)
Then from the Acquire! | Elements/cations | Element setup dialog load them into the new MDB file. This will prevent any globals, such as your wavescan flag from the Probewin.ini file from getting into the new run, but I'm pretty sure it will still bring in the crystal 2ds because those are at the element abstraction level.
Hi guys,
If you can get your hands on an ultralow C steel, or a Ti stabilised steel (even stainless steel). It will have Ti, C, N, Fe, Cr and Ni lines and enable you to set up a 2 parameter regression on the one sample to calculate the d value and the refractive index.
I was surprised at how different the D val was on my PC2 Xtal. Can't find the calcs so cannot share :(
Les
Thanks for the suggestions Les.
I've done the calcs in Excel on a line-by-line basis. Yes, I too am surprised re the differences between 'book' (aka JEOL Inspection Certificate) and 'real' d values for the LDE1 (PC1 - ca. 60Angstrom), LDE2 (PC2 - ca. 100A) and LDEB (ca. 144A) we have on our 8530F.
I won't say too much more as I would be pre-empting what I hope to present at AMAS-XIII (Hobart, Feb 2015) re my d investigations....
PS: IMHO it is a pity JEOL don't have a ca. 45Ang xtal (aka a PC0).
Cheers,
David
Unfortunately my d-spacing PfE updating saga continues >:(
I've attached the a snipit showing the log output from (yet another) brand new mdb and the crystals.dat file saved immediately before creating the new mdb.... I remain very puzzled (the polite way of saying getting very p****d off with all this now!) to know why PfE is STILL seeing the legacy d-spacings while the crystals.dat file has different (more appropriate) d values stored and saved in it.
I have not imported/loaded ANYTHING into this new mdb following John's previous posting that doing so will simply carry (unwittingly or deliberately) legacy information with the import, from an element, sample, or file setup. I fully understand this, hence my current frustration re WT* is going on!
In addition, before modifying the crystals.dat file I deliberately closed the PfE application, then editted the crystals.dat file, then restarted the PfE application, then created the brand new mdb. Then created Un 1 as the initial setup, then the first wavescan sample (WA 1). With the incorrect d-spacings (CRY2D) seemingly in place viz the log window output I haven't progressed any further.
"All" I want to do is rescan a few samples with the new d-spacings to check the KLM markers are much closer to the measured peaks than when using the default d-spacings :'(
So near, yet so far.....
David
Quote from: David Steele on December 04, 2014, 04:05:52 PM
Unfortunately my d-spacing PfE updating saga continues >:(
I've attached the a snipit showing the log output from (yet another) brand new mdb and the crystals.dat file saved immediately before creating the new mdb.... I remain very puzzled (the polite way of saying getting very p****d off with all this now!) to know why PfE is STILL seeing the legacy d-spacings while the crystals.dat file has different (more appropriate) d values stored and saved in it.
In addition, before modifying the crystals.dat file I deliberately closed the PfE application, then editted the crystals.dat file, then restarted the PfE application, then created the brand new mdb. Then created Un 1 as the initial setup, then the first wavescan sample (WA 1). With the incorrect d-spacings (CRY2D) seemingly in place viz the log window output I haven't progressed any further.
"All" I want to do is rescan a few samples with the new d-spacings to check the KLM markers are much closer to the measured peaks than when using the default d-spacings :'(
Hi David,
Well first of all, this works fine as I just tested it.
Here is the sample with the original 2d spacing:
Wa 1 wavescan sample
TakeOff = 40.0 KiloVolt = 15.0 Beam Current = 30.0 Beam Size = 0
(Magnification (analytical) = 4000), Beam Mode = Analog Spot
(Magnification (default) = 200, Magnification (imaging) = 100)
Image Shift (X,Y): -2.00, 3.00
Normal Wavescan: Step/Count Scan
Number of Data Lines: 0 Number of 'Good' Data Lines: 0
ELEM: Spectro o ka BEAM
BRAGG: 1
SPEC: 3
CRYST: WSI60
CRY2D: 61.0000
CRYK : .014830
And after editing the Crystals.dat file and creating a new probe run database, here is my sample with the newly edited 2d spacing in the crystals.dat file:
Wa 1 wavescan sample
TakeOff = 40.0 KiloVolt = 15.0 Beam Current = 30.0 Beam Size = 0
(Magnification (analytical) = 4000), Beam Mode = Analog Spot
(Magnification (default) = 200, Magnification (imaging) = 100)
Image Shift (X,Y): -2.00, 3.00
Normal Wavescan: Step/Count Scan
Number of Data Lines: 0 Number of 'Good' Data Lines: 0
ELEM: Spectro o ka BEAM
BRAGG: 1
SPEC: 3
CRYST: WSI60
CRY2D: 60.5000
CRYK : .014830
One problem I can see is that you are editing the Crystals.dat.txt file, not the Crystals.dat file! ???
OK, how do I edit the crystals.dat file without using a text editor?
In my very last attempt, I editted the crystals.dat file using Notepad++, it was saved as crystals.dat.txt (as you point out) BUT I then renamed it crystals.dat. That is the file (name) stored in the ProbeSoftware directory.
David
Quote from: David Steele on December 04, 2014, 04:30:42 PM
OK, how do I edit the crystals.dat file without using a text editor?
Any text editor will work. I use TextPad, but NotePad works fine too. Just be sure to save it as crystals.dat not crystals.dat.txt!
Quote from: David Steele on December 04, 2014, 04:30:42 PM
In my very last attempt, I editted [sic] the crystals.dat file using Notepad++, it was saved as crystals.dat.txt (as you point out) BUT I then renamed it crystals.dat. That is the file (name) stored in the ProbeSoftware directory.
Also it needs to be in the Probe Software\Probe for EPMA folder, not the Probe Software folder!
Well, you might want to double check your work because it looks like "who-man" error to me... I should know, I've made more than my share of "who-man" errors!
John is correct.... "who-man" error, or "the nut on the keyboard" if you have a more computer-oriented inclination! :-[
All working now with the appropriate d-spacings.
I have to be much more careful with Notepad+++ and how the files are saved. I suspect I've done a "Save As" and Notepad++ has added the .txt suffix. What I should do is update (any) .dat file in Notepad++ but simply "Save" it. Any additional copies (i.e. for off-probe users of PfE) should be simple copies of the file in the ProbeSoftware directory rather than saved from Notepad++....
Live and learn, and hopefully remember all these issues :)
Unfortunately my Memory seems to be increasingly more "Random" and less "Access" as time goes by....
Cheers,
David
My contributions to the crowd source:
LDE1 (nom. 60A): dcalc = 61.05 A, k = 0.013 (The JEOL inspection certificate I received gives 60.1 A, and no value for k)
LDE2 (nom. 100A): dcalc = 101.66 A, k = 0.034 (The JEOL inspection certificate I received gives 98.6 A, no value for k)
LDEB (nom. 145A): dcalc = 148.11 A, k = 0.034 (The JEOL inspection certificate I received gives 144.0A, and no value for k)
These values were determined iteratively using Excel (but not using Julien's macro, which I've only just seen - today (Dec 15th...)). I'll give Julien's macro a run sometime "soon" (i.e. before AMAS-XIII in Feb next year) and see how the sets of d and k actually compare! I presume the macro is multi-lingual, i.e. conversant with JEOL-speak L (mm) values and not just CAMECA-speak sinthetas??
Rescans in a new MDB using the above info in the crystals.dat file gives Plot! KLM markers that fit very well on the LDE1 and LDE2 crystals, but the KLMs on the LDEB using 148.11 are still a little "off". One thing I noted was a huge (2.6mm!) peak shift between BKa measured on B metal and BKa measured on BN. The B metal gives a calculated d of 150.7, whereas the BN gives a calculated d of 148.72. The latter is much closer to the values calculated from the higher order Ka peaks from Si, Al, Mg and O (using SiO2, Al2O3 and MgO), supplemented by various fluorides and pure metals (L lines....).
PS: Haven't got close to using CalcZAF, which was why I was puzzled where the peak position calculator was hiding.....
PPS: Yes curious the JEOL 100mm RC spectros use the same L mm value as the 140mm RCs! Some behind the scenes jiggery-pokery from JEOL...
Cheers,
DAvid
QUT
Does anyone have the nominal 2d spacing value for the LDE6 multilayer crystal? Also, if anyone can tell me what the PC/LDE crystals are each made of it'd be interesting to know. The only one I have info so far is PC1/LDE1 (W/Si). I'm looking for PC3/LDE3, PC2.5/LDEB, PC2/LDE2, and PC0/LDE45.
P.S. I understand the reason JEOL use a Roland circle value of 140 rather than 100 to calculate the 'mm' values is so that they are consistent for a given element across all three spectrometer types.
Quote from: Mike Matthews on December 03, 2015, 01:28:02 PM
Does anyone have the nominal 2d spacing value for the LDE6 multilayer crystal? Also, if anyone can tell me what the PC/LDE crystals are each made of it'd be interesting to know. The only one I have info so far is PC1/LDE1 (W/Si). I'm looking for PC3/LDE3, PC2.5/LDEB, PC2/LDE2, and PC0/LDE45.
P.S. I understand the reason JEOL use a Roland circle value of 140 rather than 100 to calculate the 'mm' values is so that they are consistent for a given element across all three spectrometer types.
I quote this from a preprint by Owen Neill:
(https://smf.probesoftware.com/oldpics/i66.tinypic.com/11tbs6e.jpg)
http://www.minsocam.org/msa/ammin/AM_Preprints/5370McCloyPreprintFeb.pdf
Quote from: Owen Neill on December 03, 2015, 02:29:40 PM
And yes, L-values are consistent between 140 and 100m JEOL spectros, so (for example) Fe Ka is at ~134.7mm on both types of spectros.
There is a cute little dialog in CalcZAF for calculating nominal spectrometer positions for both Cameca and JEOL (all three spectrometer types) that is accessed from the X-Ray menu as described here:
http://smf.probesoftware.com/index.php?topic=375.msg1990#msg1990
You can try different refractive indices to see the effect, or not use any refractive index correction...
Quote from: Owen Neill on December 03, 2015, 02:29:40 PM
According to a sheet I found in a drawer:
LDE1 = W/Si, 60A
LDE2 = Ni/C, 100A
LDEN = W/Si, 80A
LDE3 = Mo/B4C, 200A
LDEB = Mo/B4C, 145A
LDE5 = Cr/Sc, 80A
LDE6 = Cr/C, 120A
This is a most excellent table for the 2D spacing and compositions of these JEOL analyzing crystals!
Does anyone have a similar table for Cameca instruments PC analyzing crystals? I only have the nominal 2D spacings and refractive index values for these crystals:
"PC0" 45.0 0.006
"PC1" 60.6 0.00832
"PC2" 95.0 0.021
"PC25" 147.66 0.02
"PC3" 200.5 0.02
For the PC25 crystal I "tuned" the 2D per John Fournelle's procedure here:
http://smf.probesoftware.com/index.php?topic=197.msg1732#msg1732
It's in the attachment at the bottom of the post.
Thanks for the summary Owen, that's excellent.
John, my understanding is that both the JEOL and Cameca crystals come from the same supplier, they just name them differently, so the following are direct equivalents:
PC3 = LDE3
PC25 = LDEB
PC2 = LDE2
PC1 = LDE1
PC0 = LDE45
I'm not sure which PC, if any, is equivalent to LDE6 though.
In case anyone wants hand-crank some energy to spec positions conversions:
WDj = (24.792 x R)/(2d x E) or E = (24.792 x R)/(2d x WDj)
WDc = (12.3986 x 100000)/(2d x E) or E = (12.3986 x 100000)/(2d x WDc)
Which means that:
WDj = 0.0028 x WDc or WDc = 357.143 x WDj
To convert between wavelength and energy:
L = 12.3986/L or L = 12.3986/E
where
WDj and WDc are the JEOL and Cameca spectrometer positions respectively,
R is the Rowland circle radius in mm (160 for Cameca and 140 for all three JEOL spectrometers),
2d is the crystal lattice spacing in A,
E is the X-Ray energy in keV
L is the X-Ray wavelength in A
And if you've ever wondered where the constant 12.3986 (or so) comes from...
(https://smf.probesoftware.com/oldpics/i65.tinypic.com/28w2tyc.jpg)
How about adding the old school 127 mm Rowland circle from the ARL SEMQ?
Quote from: sckuehn on December 08, 2015, 11:51:24 AM
How about adding the old school 127 mm Rowland circle from the ARL SEMQ?
Hi Steve,
Sorry, starting in v. 10 of my software I removed all the ARL constants from my software- and you know what? I'm not going to add them back in!
Sorry. :(
Quote from: Mike Matthews on December 04, 2015, 10:03:49 AM
Thanks for the summary Owen, that's excellent.
John, my understanding is that both the JEOL and Cameca crystals come from the same supplier, they just name them differently, so the following are direct equivalents:
PC3 = LDE3
PC25 = LDEB
PC2 = LDE2
PC1 = LDE1
PC0 = LDE45
I'm not sure which PC, if any, is equivalent to LDE6 though.
I'm trying to remember the compositions of these multi-layers. I seem to remember that:
PC0 and PC1 are W/Si
PC2 is Ni/C
PC3 is Mo/B4C
I have a PC2.5 which is also Mo/B4C.
john
One more overview, building on various literature, my notes and previous answers:
Cameca JEOL d-spacing Material
name name (nm)
PC0 - 4.5 W/Si
PC1 LDE1 6 W/Si
PC2 LDE2 10 Ni/C
PC3 LDE3 20 Mo/B4C
PC2.5/LBoron LDEB 14.5 Mo/B4C (careful: up to 0.5 wt% B2O3 fluorescence)
LNitrogen LDE5 8 Cr/Sc (careful: absorption edge under N)
? LDE6 12 Cr/C
They all come from Ovonic/Ovonyx (now part of Rigaku) in Michigan*.
I wonder if there is C fluorescence from the LDE6 as well. Has anyone ever checked/seen that?
----
*From their web page: Ovonyx™ multilayer optics are the most popular light element X-ray analyzers for all wavelength dispersive spectrometer (WDS) attachments used on SEMs and in electron probe microanalysis (EPMA). Ovonyx Analyzers are sold to most major X-ray spectrometer manufacturers around the world including Cameca, Jeol, Oxford, Shimadzu, and Thermo Noran.
Current offerings:
Product series Available 2d spacings Primary elements Secondary elements Notes
"A" 60Å F,O N
"E" 90Å N
"N" 80Å & 100Å O,C,B N
"C" 100Å C B no O interface
"H" 145Å & 200Å B Be
"Y" 145Å & 200Å B Be Intensity ≥ 130%
of H Series
I am curious about details on series "E"..
Yes, LDEC seems to be an old name for LDE2. I found this: LDEC: 9.8 nm; Ni/C Layered Synthetic; Low High B-O (Kα), optimized for C analysis.
I never heard of LDE4 but I guess it must exist just for logical reasons (LDE1-6).
I would still say the Cameca equivalent to LDE5 is the LNitrogen (they offer this).
Cameca also has a Li-capable monochromator out now (see Goldschmidt 2017 abstract).
I asked Pete McSwiggen about the LDE4. This is what he said:
"In regards to the LDE4 crystal, they used to have a LDE4H. However, it seems to have been dropped as an option back at least at the beginning of the 8200 era. I do not know what happened to it, but since it is no longer offered, I assume it was an under performer."
We can quiz JEOL at M&M and maybe find out more. I am also curious why they don't offer an equivalent to PC0.
Has anyone tested / calculated the actual 2d spacing of their monochromator? How accurate are the value provided by JEOL and Cameca? How about the refractive index? Is it fixed and physically determined in each material, or is it variable from monochromator to monochromator (or even from instrument to instrument???)?
Cheers,
Julien
Quote from: Julien on January 07, 2019, 05:25:40 AM
Has anyone tested / calculated the actual 2d spacing of their monochromator? How accurate are the value provided by JEOL and Cameca? How about the refractive index? Is it fixed and physically determined in each material, or is it variable from monochromator to monochromator (or even from instrument to instrument???)?
Cheers,
Julien
Hi Julien,
Good questions. Yes, John Fournelle has done this.
See the PPT attached to this post (need to login to see attachments):
https://smf.probesoftware.com/index.php?topic=197.msg1732#msg1732
Also yes, the refractive index is determined by the composition and layer thicknesses of the multi-layer material.
This window in CalcZAF allows one to see the effect of the refractive index on the spectrometer position:
https://smf.probesoftware.com/index.php?topic=598.msg4347#msg4347
The "K index" is the refractive index from the CRYSTALS.DAT file in the ProgramData\Probe Software\Probe for EPMA folder.
john
JEOL provides an inspection certificate stating the d-spacing for each LDE monochromator installed but not their refractive index. The values can vary quite a bit from machine to machine and crystal to crystal in my experience.
For example, on my new machine I have LDE1: 6.04 nm; LDE2: 9.86 nm; LDE6L: 11.86 nm. I have somewhere values from some other instruments. Let's see what I can dig up.
I haven't had a chance to cross-check mine yet but will report back what I find when I get to it.
I have been asked to add my 2 cents here...
Recall that one typically peaks on an element of interest on a specific spectrometer bearing a specific crystal. Say F Ka on a nominal 45 A 2d diffraction. Thus the software will "automatically" set the spectrometer position, correctly showing the F Ka peak at the "published" position (whether sin theta, mm, A or eV). 2d and K refraction value are essentially non-observable. The point of having a correct 2d with correct K refraction value are that when one wishes to see higher order markers, they will fall in the right place. That is what I found years ago with the SX51 and good old PfW v9 (still running it on SX51).
A test to tell me if this is relevant. With say 60A diffractor, peak on O Ka on an aluminosilicate. Then in PHA mode integral, do a detailed slow wavescan, for whole spectrometer range, and see if the 3rd order higher order peak markers for Al and Si (and maybe other elements too) line up with the observed peaks. If they do, hurrah, and no need to do anything. If they don't, then 2d and K need some adjustment.
John
Bringing this topic forward because a colleague of ours recently had an issue where the spectrometer position for oxygen on their LDE1 Bragg crystal was not being calculated correctly. In fact it was off by ~2 mm!
Basically they need to perform the measurements documented by John Fournelle here:
https://academic.oup.com/mam/article-abstract/12/S02/836/6916142
I'll ask John for his Powerpoint for this procedure and post it here later...
In the meantime they can decrease the sensitivity of this peak offset error by editing this parameter in their SCALERS.DAT file on line 34:
400. 400. 400. 400. 400. "Spec offset warning factors"
The sensitivity is calculated for each spectrometer as: (hilimit - lolimit) / specoffsetwarningfactor
So to (temporarily) decrease the sensitivity of this warning simply edit the 400 value on that spectrometer to a smaller number, say 300 and they shouldn't get any more warnings.
I believe we discussed this earlier in this thread... The real (mechanical) position of the peaks will first depend on the spectrometer initialisation (check min/max limit) and non-linearity (i.e., check position of several X-ray peak and apply a polynomial fit to the X-ray position to match the expected theoretical value). At least that's how JEOL is doing it...
Then, the problem is of course the accuracy of the 2d-spacing value and its famous refractive index "k" (see for instance S. Reed's book). In an earlier post, I had given a spreadsheet to calculate the 2d and the k index from a set of measurement to be done on each individual EPMA, quoted below. I guess not all diffracting monochromators are born equal ;)
See the attached spreadsheet. It contains macro and use the Solver from Microsoft Excel to fit the 2d and k values based on a set of X-ray position measurement at different diffraction order n = 1 to 4. Instruction in the first sheet.
Julien
Quote from: Julien on November 24, 2014, 04:17:35 PMAlright, after a few hours of WDS scan on grand'ma JEOL-8600 (26 years old!), I got some results on the 2d-k evaluation on my available multilayers. Results on LDE1 (60 Å) are pretty consistant, independent on the X-ray line / order I choose for the regression. However, I cannot tell this for the other two large-2d spectro I have (LDEC ~100Å and LDEB ~150Å). Here it is (details in the spreadsheet):
- LDE1 (60 Å): 2d = 61.3 Å / k = 0.013
- LDEC (100 Å): 2d = 102.5 Å / k = 0.028
- LDEB (150 Å): 2d = 149.2 Å / k = 0.035
Now, if I exclude some "badly defined (high order) peaks"...
- LDE1 (60 Å): 2d = 61.3 Å / k = 0.014
- LDEC (100 Å): 2d = 102.8 / k = 0.031
- LDEB (150 Å): 2d = 150.0 / k = 0.041
Note that these values are NOT corrected for possibly dynamic (mechanical) shift... I cannot easily verify this (suggestions are welcome for this matter...), although if I assume a shift similar to the other crystals available (PET and TAP for spectrometer with LDEC and LDEB, TAP for spectrometer with LDE1), then here are the results:
- LDE1 (60 Å): 2d = 61.4 Å / k = 0.013
- LDEC (100 Å): 2d = 102.7 Å / k = 0.028
- LDEB (150 Å): 2d = 149.4 Å / k = 0.035
("of course" this shift chiefly affects the 2d of the crystal, not so much the k...)
See the XL spreadsheets for the results (one is a modified copy of the XL macro I wrote - see my former comment, the other are the acquisition results [peak positions]; these results are NOT corrected for possible dynamic shift, which are in the order of 0.1-0.2 mm on my JEOL-8600). I got these results using a high-beam current (most of them 200 nA, some 100 nA), with 2 to 4 seconds counting time (longer on high-order lines), and with a step of 0.1 mm or 0.00035 sin-theta (some 0.25 mm = 0.00090 sin-theta). These could have been refined using a smaller step size and longer counting time, but I did not have enough time to do this today... Also, keep in mind that ALL my monochromators are "normal" area monochromator... Hence the difficulty to get good precision on X-ray line above 3rd-4th order... Even on pure metals for L-lines...
@John Fournelle: maybe, can you suggest the conditions you've used for your WDS scan?
And for comparison, here are the data that John Fournelle mention in his PowerPoint (slide 19):
- PC0 (45 Å): old = 44 Å, 0.01483 => NEW: 44 Å, 0.01
- PC1 (60 Å): old = 61 Å, 0.01 => NEW: 62.1 Å, 0.02
- PC2 (100 Å): old = 95.2 Å, 0.013 => NEW: 98.5 Å, 0.033
- PC3 (200 Å): old = 200 Å, 0.01 => NEW: 204 Å, 0.04
Comments and additional data from other labs are more than welcome!
Julien
Thank-you Julien. I will send this to our colleague.
Two questions on JEOL LDE crystals:
1. What is the 2d spacing for the JEOL LDEC? I see 100A but also 200A elsewhere. Which is correct? 😕
2. What is the refractive index (k) for LDEB? The default K value (0.01) I have for LDEB is clearly too low!
John, Julien, -
Thank you for all your help and advice. I have used the values Julien found/calculated for the LDE1 (2d = 61.4A and k= 0.013) and have now got an offset of just -0.0624 mm. An incredible improvement over the close to 2mm offset I had before.
(my first forum post! and I finally figured out how!)
Quote from: irisbuisman on November 27, 2024, 09:05:40 AMJohn, Julien, -
Thank you for all your help and advice. I have used the values Julien found/calculated for the LDE1 (2d = 61.4A and k= 0.013) and have now got an offset of just -0.0624 mm. An incredible improvement over the close to 2mm offset I had before.
(my first forum post! and I finally figured out how!)
Very nice!
I'd still like to get an answer to my questions here from anyone:
https://smf.probesoftware.com/index.php?topic=375.msg12962#msg12962
Quote from: John Donovan on November 08, 2024, 10:12:45 AMTwo questions on JEOL LDE crystals:
1. What is the 2d spacing for the JEOL LDEC? I see 100A but also 200A elsewhere. Which is correct? 😕
It is 100A and uses V/C. I don't know where the 200A comes from, probably a type. With a 'd' of 200A you would not reach C Ka on a JEOL spectrometer.
Quote from: John Donovan on November 08, 2024, 10:12:45 AM2. What is the refractive index (k) for LDEB? The default K value (0.01) I have for LDEB is clearly too low!
Julien got the following for his Boulder probe (see first page of this thread).
- LDEB (150 Å): 2d = 149.4 Å / k = 0.035
Quote from: Anette von der Handt on December 02, 2024, 12:42:42 PMQuote from: John Donovan on November 08, 2024, 10:12:45 AMTwo questions on JEOL LDE crystals:
1. What is the 2d spacing for the JEOL LDEC? I see 100A but also 200A elsewhere. Which is correct? 😕
It is 100A and uses V/C. I don't know where the 200A comes from, probably a typo. With a 'd' of 200A you would not reach C Ka on a JEOL spectrometer.
Quote from: John Donovan on November 08, 2024, 10:12:45 AM2. What is the refractive index (k) for LDEB? The default K value (0.01) I have for LDEB is clearly too low!
Julien got the following for his Boulder probe (see first page of this thread).
- LDEB (150 Å): 2d = 149.4 Å / k = 0.035
This is very helpful, thank-you!
Here is what we have as defaults for the LDE type Bragg crystals in our CRYSTALS.DAT file:
"WSi45" 45.0 0.010 "o" "ka"
"LDE45" 45.0 0.010 "o" "ka"
"PC0" 45.0 0.006 "o" "ka"
"WSi55" 55.0 0.014 "o" "ka"
"LDE1L" 60.2 0.014 "o" "ka"
"WSi60" 61.0 0.01483 "o" "ka"
"LDE1" 61.1 0.01 "o" "ka"
"LDE1H" 62.5 0.008 "c" "ka"
"WSi63" 63.0 0.015 "o" "ka"
"LDE1L" 60.2 0.014 "o" "ka"
"PC1" 60.6 0.00832 "o" "ka"
"NiCrBN" 65.0 0.016 "o" "ka"
"LDE5L" 80.1 0.018 "c" "ka"
"NiC" 80.2 0.018 "c" "ka"
"LSM" 80.0 0.03 "c" "ka"
"PC2" 95.0 0.021 "c" "ka"
"OV95" 96.8 0.02 "c" "ka"
"STE" 98.0 0. "c" "ka"
"LDE2" 98.0 0.01 "c" "ka"
"LDE2H" 98.0 0.01 "c" "ka"
"LDEC" 100. 0.04 "c" "ka"
"PbSd" 100.6 0. "c" "ka"
"PbSTEA" 100.6 0. "c" "ka"
"ODPB" 100.7 0.0175 "c" "ka"
"LDE6H" 120.0 0.02 "c" "ka"
"WC144" 144.0 0.03 "b" "ka"
"LDEB" 145.0 0.035 "b" "ka"
"PC25" 147.66 0.02 "b" "ka"
"OV160" 160.0 0.03 "b" "ka"
"MoB4C" 194.57 0.04 "b" "ka"
"OV200" 197.4 0.04 "b" "ka"
"LDE3H" 200.0 0.02 "be" "ka"
"PC3" 200.5 0.02 "be" "ka"
Any other suggestions?